Polyamides with pendent pigments and related methods

ABSTRACT

A nonlimiting example method for synthesizing a pigment-pendent polyamide (PP-polyamide) may comprise: functionalizing metal oxide particles bound to a pigment particle with a compound having an epoxy to produce a surface treated pigment having a pendent epoxy; and reacting the pendent epoxy with a polyamide to yield the PP-polyamide. Another nonlimiting example method for synthesizing a PP-polyamide may comprise: functionalizing metal oxide particles bound to a pigment particle with a silica particle having a carboxylic acid surface treatment to produce a surface treated pigment having a pendent carboxylic acid; converting the pendent carboxylic acid to a pendent acid chloride; and reacting the pendent acid chloride with a polyamide to yield the PP-polyamide. Said PP-polyamide may be useful in producing objects by methods that include melt extrusion, injection molding, compression molding, melt spinning, melt emulsification, spray drying, cryogenic milling, freeze drying polymer dispersions, and precipitation of polymer dispersions.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority under 35 U.S.C. §119 from U.S. Provisional Patent Application 62/897,534, filed on Sep.9, 2019 and U.S. Patent Application Publication 2021/0070938, each ofwhich is incorporated herein by reference in its entirety.

TECHNICAL FIELD

The present disclosure relates to compositions, synthesis methods, andapplications of polyamides having pigments pendent from the backbone ofthe polyamide. For example, particles may comprise polyamides havingpigments pendent from the backbone of the polyamide.

BACKGROUND

Thermoplastic polymers are often used to make extruded objects likefilms, bags, particles, and filaments. One example of a thermoplasticpolymer is a polyamide. Polyamides like nylons are off-white coloredpolymers that have the ability to withstand elevated or low temperatureswithout loss of physical properties. Therefore, objects formed withpolyamides can be used in demanding applications like power tools,automotive parts, gears, and appliance parts. In some instances, theapplication may call for the polyamide-made part to be colored. Becausepigments are particulates, pigments can be difficult to homogeneouslymix in the polyamide, which causes the coloring of the resultant part tobe uneven.

One application where homogeneous incorporation of pigments isespecially important is the rapidly growing technology area ofthree-dimensional (3-D) printing, also known as additive manufacturing.Although 3-D printing has traditionally been used for rapid prototypingactivities, this technique is being increasingly employed for producingcommercial and industrial objects, which may have entirely differentstructural and mechanical tolerances than do rapid prototypes.

3-D printing operates by depositing either (a) small droplets or streamsof a melted or solidifiable material or (b) powder particulates inprecise deposition locations for subsequent consolidation into a largerobject, which may have any number of complex shapes. Such deposition andconsolidation processes typically occur under the control of a computerto afford layer-by-layer buildup of the larger object. In a particularexample, consolidation of powder particulates may take place in a 3-Dprinting system using a laser to promote selective laser sintering(SLS).

Powder particulates usable in 3-D printing include thermoplasticpolymers, including thermoplastic elastomers, metals and othersolidifiable substances. One example thermoplastic polymer is nylon.Nylons are off-white colored polymers that have the ability to withstandelevated or low temperatures without loss of physical properties.Therefore, nylons can be used in demanding applications like powertools, automotive parts, gears, and appliance parts.

When using a particulate pigment in 3-D printing, the particulatesshould be evenly dispersed throughout the small melted droplets or thepower particulate, or the coloring of the final object will be uneven.

SUMMARY OF INVENTION

The present disclosure relates to compositions, synthesis methods, andapplications of polyamides having pigments pendent from the backbone ofthe polyamide. For example, particles may comprise polyamides havingpigments pendent from the backbone of the polyamide.

Described herein is a method comprising: functionalizing metal oxideparticles that are bound to a pigment particle with a compound having anepoxy to produce a surface treated pigment having a pendent epoxy; andreacting the pendent epoxy with a polyamide to yield a pigment-pendentpolyamide (PP-polyamide).

Described herein is a method comprising: functionalizing metal oxideparticles that are bound to a pigment particle with a silica particlehaving a carboxylic acid surface treatment to produce a surface treatedpigment having a pendent carboxylic acid; converting the pendentcarboxylic acid to a pendent acid chloride; and reacting the pendentacid chloride with a polyamide to yield a PP-polyamide.

Described herein is a composition comprising: a polyamide having apigment pendent from a backbone of the polyamide, wherein the pigmentcomprises metal oxide particles on the surface of a pigment particle.

Also described herein are objects comprising the foregoing compositions.

Described herein is a method comprising: mixing a mixture comprising apolyamide having a PP-polyamide, a carrier fluid that is immiscible withthe PP-polyamide, and optionally an emulsion stabilizer at a temperaturegreater than a melting point or softening temperature of thePP-polyamide and at a shear rate sufficiently high to disperse thePP-polyamide in the carrier fluid; and cooling the mixture to below themelting point or softening temperature of the PP-polyamide to formsolidified particles comprising the PP-polyamide and, when present, theemulsion stabilizer associated with an outer surface of the solidifiedparticles.

Described herein is a composition comprising: particles comprising apolyamide having a PP-polyamide and having a circularity of about 0.90to about 1.0. Said particles may further comprise one or more emulsionstabilizers associated with an outer surface of the particles.

Also disclosed herein are methods that comprise: depositing saidparticles (that comprise the PP-polyamide) optionally in combinationwith other thermoplastic polymer particles upon a surface in a specifiedshape; and once deposited, heating at least a portion of the particlesto promote consolidation thereof and form a consolidated body.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are included to illustrate certain aspects of thedisclosure, and should not be viewed as exclusive configurations. Thesubject matter disclosed is capable of considerable modifications,alterations, combinations, and equivalents in form and function, as willoccur to those skilled in the art and having the benefit of thisdisclosure.

The FIGURE a flow chart of a nonlimiting example method 100 of thepresent disclosure.

DETAILED DESCRIPTION

The present disclosure relates to compositions, synthesis methods, andapplication methods of polyamides having a pigment pendent from thebackbone of the polyamide, also referred to herein as an polyamidehaving pendent pigments or PP-polyamide. Because the polyamides arefunctionalized with the pigment particles, objects that incorporate thePP-polyamide will have a more evenly dispersed pigment.

The present disclosure also relates to particles comprising polyamideshaving a pigment pendent from the backbone of the polyamide (alsoreferred to herein as a pigment-pendent polyamide or PP-polyamide) andrelated methods. More specifically, the present disclosure includesmethods of making highly spherical polymer particles comprising the oneor more PP-polyamides and optionally one or more other thermoplasticpolymers. Said polymer particles may be useful, among other things, asstarting material for additive manufacturing.

The polymer particles described herein may be, for example, produced bymelt emulsification methods where one or more PP-polyamides andoptionally one or more additional thermoplastic polymers are dispersedas a melt in a carrier fluid that is immiscible with the PP-polyamideand additional thermoplastic polymers, if used. A sufficient amount ofshear is applied to the mixture to cause the polymer melt to formdroplets in the carrier fluid.

Because the pigment is pendent from the backbone of the polyamide,objects produced by additive manufacturing methods that include theseparticles should maintain an even color over time because the pigmentcannot migrate within the object.

Definitions and Test Methods

As used herein, the term “pigment” refers to a particle that absorbsand/or refracts ultraviolet or visible light. As used herein, a “surfacetreated pigment” refers to a pigment having oxide particles chemicallybonded and/or physically bonded to the surface of the pigment particle.

As used herein, the term “immiscible” refers to a mixture of componentsthat, when combined, form two or more phases that have less than 5 wt %solubility in each other at ambient pressure and at room temperature orthe melting point of the component if it is solid at room temperature.For example, polyethylene oxide having 10,000 g/mol molecular weight isa solid at room temperature and has a melting point of 65° C. Therefore,said polyethylene oxide is immiscible with a material that is liquid atroom temperature if said material and said polyethylene oxide have lessthan 5 wt % solubility in each other at 65° C.

As used herein, the term “thermoplastic polymer” refers to a plasticpolymer material that softens and hardens reversibly on heating andcooling. Thermoplastic polymers encompass thermoplastic elastomers.

As used herein, the term “elastomer” refers to a copolymer comprising acrystalline “hard” section and an amorphous “soft” section. In the caseof a polyurethane, the crystalline section may include a portion of thepolyurethane comprising the urethane functionality and optional chainextender group, and the soft section may include the polyol, forinstance.

As used herein, the term “polyurethane” refers to a polymeric reactionproduct between a diisocyanate, a polyol, and an optional chainextender.

As used herein, the term “oxide” refers to both metal oxides andnon-metal oxides. For purposes of the present disclosure, silicon isconsidered to be a metal.

As used herein, the terms “associated,” “association,” and grammaticalvariations thereof between emulsion stabilizers and a surface refers tochemical bonding and/or physical adherence of the emulsion stabilizersto the surface. Without being limited by theory, it is believed that theassociations described herein between polymers and emulsion stabilizersare primarily physical adherence via hydrogen bonding and/or othermechanisms. However, chemical bonding may be occurring to some degree.

As used herein, the term “embed” relative to nanoparticles and a surfaceof a polymer particle refers to the nanoparticle being at leastpartially extended into the surface such that polymer is in contact withthe nanoparticle to a greater degree than would occur if thenanoparticle were simply laid on the surface of the polymer particle.

Herein, D10, D50, D90, and diameter span are primarily used herein todescribe particle sizes. As used herein, the term “D10” refers to adiameter at which 10% of the sample (on a volume basis unless otherwisespecified) is comprised of particles having a diameter less than saiddiameter value. As used herein, the term “D50” refers to a diameter atwhich 50% of the sample (on a volume basis unless otherwise specified)is comprised of particles having a diameter less than said diametervalue. As used herein, the term “D90” refers to a diameter at which 90%of the sample (on a volume basis unless otherwise specified) iscomprised of particles having a diameter less than said diameter value.

As used herein, the terms “diameter span” and “span” and “span size”when referring to diameter provides an indication of the breadth of theparticle size distribution and is calculated as (D90−D10)/D50 (againeach D-value is based on volume, unless otherwise specified).

Particle size can be determined by light scattering techniques using aMalvern MASTERSIZER™ 3000 or analysis of optical digital micrographs.Unless otherwise specified, light scattering techniques are used foranalyzing particle size.

For light scattering techniques, the control samples were glass beadswith a diameter within the range of 15 μm to 150 μm under the tradenameQuality Audit Standards QAS4002™ obtained from Malvern Analytical Ltd.Samples were analyzed as dry powders, unless otherwise indicated. Theparticles analyzed were dispersed in air and analyzed using the AERO Sdry powder dispersion module with the MASTERSIZER™ 3000. The particlesizes were derived using instruments software from a plot of volumedensity as a function of size.

Particle size measurement and diameter span can also be determined byoptical digital microscopy. The optical images are obtained using aKeyence VHX-2000 digital microscope using version 2.3.5.1 software forparticle size analysis (system version 1.93).

As used herein, when referring to sieving, pore/screen sizes aredescribed per U.S.A. Standard Sieve (ASTM E11-17).

As used herein, the terms “circularity” and “sphericity” relative to theparticles refer to how close the particle is to a perfect sphere. Todetermine circularity, optical microscopy images are taken of theparticles. The perimeter (P) and area (A) of the particle in the planeof the microscopy image is calculated (e.g., using a SYSMEX FPIA 3000particle shape and particle size analyzer, available from MalvernInstruments). The circularity of the particle is C_(EA)/P, where C_(EA)is the circumference of a circle having the area equivalent to the area(A) of the actual particle.

As used herein, the term “sintering window” refers to the differencebetween the melting temperature (Tm) onset and the crystallizationtemperature (Tc) onset, or (Tm−Tc) onset. Tm, Tm (onset), Tc, and Tc(onset) are determined by differential scanning calorimetry per ASTME794-06(2018) with a 10° C./min ramp rate and a 10° C./min cool rate.

As used herein, the term “shear” refers to stirring or a similar processthat induces mechanical agitation in a fluid.

As used herein, the term “aspect ratio” refers to length divided bywidth, wherein the length is greater than the width.

The melting point of a polymer, unless otherwise specified, isdetermined by ASTM E794-06(2018) with 10° C./min ramping and coolingrates.

The softening temperature or softening point of a polymer, unlessotherwise specified, is determined by ASTM D6090-17. The softeningtemperature can be measured by using a cup and ball apparatus availablefrom Mettler-Toledo using a 0.50 gram sample with a heating rate of 1°C./min.

Angle of repose is a measure of the flowability of a powder. Angle ofrepose measurements were determined using a Hosokawa Micron PowderCharacteristics Tester PT-R using ASTM D6393-14 “Standard Test Methodfor Bulk Solids” Characterized by Carr Indices.”

Hausner ratio (H_(r)) is a measure of the flowability of a powder and iscalculated by H_(r)=ρ_(tap)/ρ_(bulk), where ρ_(bulk) is the bulk densityper ASTM D6393-14 and ρ_(tap) is the tapped density per ASTM D6393-14.

As used herein, viscosity of carrier fluids are the kinematic viscosityat 25° C., unless otherwise specified, measured per ASTM D445-19. Forcommercially procured carrier fluids (e.g., PDMS oil), the kinematicviscosity data cited herein was provided by the manufacturer, whethermeasured according to the foregoing ASTM or another standard measurementtechnique.

Pigment-Pendent Polyamides

Generally, the compositions, synthesis methods, and application methodsof the present disclosure use a linker that chemically bonds to theoxide particles of the surface treated pigment to a nitrogen of thepolyamide. The result is a PP-polyamide. Because surface treatedpigments have several oxide particles on the surface, the surfacetreated pigment particles can act as crosslinkers for the polyamides.

Examples of polyamides include, but are not limited to, polycaproamide(nylon 6, polyamide 6, or PA6), poly(hexamethylene succinamide) (nylon4,6, polyamide 4,6, or PA4,6), polyhexamethylene adipamide (nylon 6,6,polyamide 6,6, or PA6,6), polypentamethylene adipamide (nylon 5,6,polyamide 5,6, or PA5,6), polyhexamethylene sebacamide (nylon 6,10,polyamide 6,10, or PA6,10), polyundecaamide (nylon 11, polyamide 11, orPA11), polydodecaamide (nylon 12, polyamide 12, or PA12),polyhexamethylene terephthalamide (nylon 6T, polyamide 6T, or PA6T),nylon 10,10 (polyamide 10,10 or PA10,10), nylon 10,12 (polyamide 10,12or PA10,12), nylon 10,14 (polyamide 10,14 or PA10,14), nylon 10,18(polyamide 10,18 or PA10,18), nylon 6,18 (polyamide 6,18 or PA6,18),nylon 6,12 (polyamide 6,12 or PA6,12), nylon 6,14 (polyamide 6,14 orPA6,14), nylon 12,12 (polyamide 12,12 or PA12,12), semi-aromaticpolyamide, aromatic polyamides (aramides), and the like, and anycombination thereof. Copolyamides may also be used. Examples ofcopolyamides include, but are not limited to, PA 11/10,10, PA 6/11, PA6,6/6, PA 11/12, PA 10,10/10,12, PA 10,10/10,14, PA 11/10,36, PA11/6,36, PA 10,10/10,36, PA 6T/6,6, and the like, and any combinationthereof. Examples of polyamide elastomers include, but are not limitedto, polyesteramide, polyetheresteramide, polycarbonate-esteramide, andpolyether-block-amide elastomers. Herein, a polyamide followed by asingle number is a polyamide having that number of backbone carbonsbetween each nitrogen. A polyamide followed by a first number commasecond number is a polyamide having the first number of backbone carbonsbetween the nitrogens for the section having no pendent ═O and thesecond number of backbone carbons being between the two nitrogens forthe section having the pendent ═O. By way of nonlimiting example, nylon6,10 is [NH—(CH₂)₆—NH—CO−(CH₂)₈—CO]_(n). A polyamide followed bynumber(s) backslash number(s) are a copolymer of the polyamidesindicated by the numbers before and after the backslash.

Pigments may impart a color, a metallic color, and/or a pearlescentcolor such as gold, silver aluminum, bronze, gold bronze, stainlesssteel, zinc, iron, tin and copper pigments to the polyamide. Examples ofpigments include, but are not limited to, synthetic mica (e.g.,fluorphlogopite), natural mica (e.g., muscovite), talc, sericite,kaolin, glass, SiO₂ flakes, Al₂O₃ flakes, glass flakes, acicularpigments (e.g., BiOCl, colored glass fibers, α-Fe₂O₃, and α-FeOOH),CaSO₄, iron oxides, chromium oxides, carbon black, metal effect pigments(e.g., Al flakes and bronzes), optically variable pigments (OVPs),liquid crystal polymer pigments (LCPs), holographic pigments, and thelike, and any combination thereof.

Examples of metal oxides that may be coating the surface of a pigmentinclude, but are not limited to, titanium dioxide, titanium suboxides,titanium oxynitrides, Al₂O₃, Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO,zirconium oxide, iron titanium oxides (iron titanates), other metaloxides, and the like, and any combination thereof. Preferred metaloxides include TiO₂ and/or Fe₂O₃.

Surface treated pigments may be any combination of the foregoingpigments with one or more metal oxides, alone or in a mixture in auniform layer or in successive layers. For example, the surface treatedpearlescent pigments may be pigments based on platelet-shaped,transparent or semitransparent substrates like sheet silicates, whichare coated with colored or colorless metal oxides like titanium oxidesand iron oxides, alone or in a mixture in a uniform layer or insuccessive layers. Particularly preferred surface treated pigmentscontain TiO₂-coated mica, Fe₂O₃-coated mica, TiO₂/Fe₂O₃-coated mica, andany combination thereof.

Examples of commercially available surface treated pigments include, butare not limited to, REFLEX™ pigments (synthetic mica-based pearlescentpigments, available from CQV), IRIODIN™ (mica-based, metal oxide-coatedpearlescent pigments, available from Merck) (e.g., IRIODIN™ 300 “GoldPearl” and IRIODIN™ 100 “Silver Pearl”), SUNGEM™ (glass platelet-basedpigments, available from Sun Chemical), SUNMICA™ (mica-based pigments,available from Sun Chemical), SYNCRYSTAL™ (metal oxide coated syntheticfluorphlogopite flakes, available from Eckart), and the like, and anycombination thereof. Other metallic color pearlescent pigments fromMerck include TIMIRON® Bronze MP60 with a D50 volume average particlesize (50% of the pigments have a volume size of less than the statedsize) of 22-37 microns, TIMIRON® Copper MP-65 D50 size of 22-37 microns,COLORONA® Oriental Beige D50 size of 3-10 microns, COLORONA® AborigineAmber D50 size of 18-25 microns, COLORONA® Passion Orange with D50 sizeof 18-25 microns, COLORONA® Bronze Fine of D50 size of 7-14, COLORONA®Bronze with D50 size of 18-25 microns, COLORONA® Bronze Sparkle of D50size of 28-42 microns, COLORONA® Copper Fine with D50 size of 7-14microns, COLORONA® Copper with D50 size of 18-25, COLORONA® CopperSparkle with D50 size of 25-39 microns, COLORONA® Red Brown with D50size of 18-25 microns, COLORONA® Russet with D50 size of 18-25 microns,COLORONA® Tibetan Ochre with D50 size of 18-25 microns, COLORONA® SiennaFine with D50 size of 7-14 microns, COLORONA® Sienna with D50 size of18-25 microns, COLORONA® Bordeaux with D50 size of 18-25 microns,COLORONA® Glitter Bordeaux, COLORONA® Chameleon with D50 size of 18-25microns. Also suitable are Merck mica based pigments with metal oxideparticle coatings such as the Merck silvery white pigments includingTIMIRON® Super Silk MP-1005 with D50 size of 3-10 microns, TIMIRON®Super Sheen MP-1001 with D50 size of 7-14 microns, TIMIRON® Super SilverFine with D50 size of 9-13 microns, TIMIRON® Pearl Sheen MP-30 with D50size of 15-21 microns, TIMIRON® Satin MP-11171 with D50 size of 11-20microns, TIMIRON® Ultra Luster MP-111 with D50 size of 18-25 microns,TIMIRON® Star Luster MP-111 with D50 size of 18-25 microns, TIMIRON®Pearl Flake MP-10 with D50 size of 22-37 microns, TIMIRON® Super Silverwith D50 size of 17-26 microns, TIMIRON® Sparkle MP-47 with D50 size of28-38 microns, TIMIRON® Arctic Silver with D50 size of 19-25 microns,XIRONA® Silver with D50 size of 15-22 microns, RONASTAR® Silver with D50size of 25-45 microns, and the like, and any combination thereof. Forvery bright colors, examples from Merck include COLORONA® Carmine Redwith D50 size of 10-60 microns giving a Red lustrous effect, COLORONA®Magenta with D50 size of 18-25 microns, giving a pink-violet lustrouseffect, COLORONA® Light Blue with D50 size of 18-25 microns, to give alight blue lustrous effect, COLORONA® Dark Blue with D50 size of 18-25microns to give a dark blue lustrous effect, COLORONA® Majestic Greenwith 18-25 microns to give a green lustrous color, COLORONA® BrilliantGreen of D5 19-26 microns to give a Green-golden lustrous color,COLORONA® Egyptian Emerald of D50 18-25 microns to give a dark greenlustrous effect, COLORONA® Patagonian Purple of 18-25 microns size togive a purple lustrous effect, and the like, and any combinationthereof. Mica based special effect pigments having a D50 from about 18microns to about 50 microns from Eckart may also be used, such asDORADO® PX 4001, DORADO® PX 4261, DORADO® PX 4271, DORADO® PX 4310,DORADO® PX 4331, DORADO® PX 4542, PHOENIX® XT, PHOENIX® XT 2001,PHOENIX® XT 3001, PHOENIX® XT 4001, PHOENIX® XT 5001, PHOENIX® PX 1000,PHOENIX® PX 1001, PHOENIX® PX 1221, PHOENIX® PX 1231, PHOENIX® PX 1241,PHOENIX® PX 1251, PHOENIX® PX 1261, PHOENIX® PX 1271, PHOENIX® PX 1310,PHOENIX® PX 1320, PHOENIX® PX 1502, PHOENIX® PX 1522, PHOENIX® PX 1542,PHOENIX® PX 2000, PHOENIX® PX 2000 L, PHOENIX® PX 2001, PHOENIX® PX2011, PHOENIX® PX 2021, PHOENIX® PX 2221, PHOENIX® PX 2231, PHOENIX® PX2241, PHOENIX® PX 2251, PHOENIX® PX 2261, PHOENIX® PX 2271, PHOENIX® PX3001, PHOENIX® PX 4000, PHOENIX® PX 4001, PHOENIX® PX 4221, PHOENIX® PX4231, PHOENIX® PX 4241, PHOENIX® PX 4251, PHOENIX® PX 4261, PHOENIX® PX4271, PHOENIX® PX 4310, PHOENIX® PX 4320, PHOENIX® PX 4502, PHOENIX® PX4522, PHOENIX® PX 4542, PHOENIX® PX 5000, PHOENIX® PX 5001, PHOENIX® PX5310, PHOENIX® PX 5331, and the like, and any combination thereof.Special effect pigments such as Silberline aluminum flake pigments maybe used, such as 16 micron DF-1667, 55 micron DF-2750, 27 micronDF-3500, 35 micron DF-3622, 15 micron DF-554, 20 micron DF-L-520AR, 20micron LED-1708AR, 13 micron LED-2314AR, 55 micron SILBERCOTE™ PC 0452Z,47 micron SILBERCOTE™ PC 1291X, 36 micron SILBERCOTE™, 36 micronSILBERCOTE™ PC 3331X, 31 micron SILBERCOTE™ PC 4352Z, 33 micronSILBERCOTE™ PC 4852X, 20 micron SILBERCOTE™ PC 6222X, 27 micronSILBERCOTE™ PC 6352Z, 25 micron SILBERCOTE™ PC 6802X, 14 micronSILBERCOTE™ PC 8152Z, 14 micron SILBERCOTE™ PC 8153X, 16 micronSILBERCOTE™ PC 8602X, 20 micron SILVET®/SILVEX® 890 Series, 16 micronSILVET®/SILVEX® 950 Series, and the like, and any combination thereof.

Surface treated pigments may have an average diameter (or D50) of about1 micron to about 500 microns (or about 1 micron to about 25 microns, orabout 5 microns to about 50 microns, or about 25 microns to about 200microns, or about 100 microns to about 300 microns, or about 250 micronsto about 500 microns). Without being limited by theory, it is believedthat larger pigment particles impart greater coloring, metallic, and/orpearlescent effects to the polyamide.

Scheme 1 below is a first nonlimiting example synthesis of aPP-polyamide. More specifically, a difunctional linkage reagentcontaining for example an alkoxysilane end group and a glycidylfunctional group. The alkoxysilane group (illustrated with Si(—OCH₃)₃groups where one or more of such groups may be hydrolyzed to —OH groups)is coupled to the surface of the oxide particles (MOx particles) on thesurface of the pigment. While the silane is shown as coupling only tothe metal oxide particles, the silane may also couple to the surface ofthe pigment depending on the composition of the pigment. Then, the epoxyof the glycidyl moiety reacts with the nitrogen of the amide in thepolyamide (illustrated using nylon 6) to yield a PP-polyamide. While theepoxy is illustrated as a terminal epoxy, the difunctional linkagereagent may have one or more glycidyl functional groups (or epoxygroups) that are terminal, pendent, or include both terminal and pendentof such groups. As illustrated, the pigment is chemically linked to fourpolyamide chains, which illustrates that the pigment may also be acrosslinker.

Examples of silanes having a glycidyl moiety include, but are notlimited to, (3-glycidoxypropyl)trimethoxysilane,(3-glycidoxypropyl)triethoxysilane,diethoxy(3-glycidyloxypropyl)methylsilane and1,3-bis(3-dlycidyloxypropyl)tetramethylsiloxane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane,3-glycidoxypropyl methyldiethoxysilane, 5,6-epoxyhexyltriethoxysilane,and the like, and any combination thereof.

The silane coupling reaction can be performed by known methods. Forexample, as outlined in reference by X. Guillory et al. called GlycidylAlkoxysilanc Reactivities Towards Simple Nucleophiles in Organic Mediafor Improved Molecular Structure Definition in Hybrid Materials in RoyalSociety of Chemistry Advances 2016, 6, 74087-74099. The outcome of thereactions are highly dependent on the reaction conditions; selection ofsolvent whether it be aqueous, organic or ionic liquid media,temperature concentration, catalyst and acidic or basic conditions. Alsofrom the cited U.S. Pat. No. 7,998,649, the metallic oxide coated micapigment that is a silica or titania particle surface is reacted with(3-glycidoxypropyl)trimethoxysilane or(3-glycidoxypropyl)triethoxysilane ordiethoxy(3-glycidyloxypropyl)methylsilane or1,3-bis(3-dlycidyloxypropyl)tetramethylsiloxane in a molar ratio of 0.85to 0.15 with the appropriate amount of ethanol or methanol, water, andammonia to prepare the epoxide containing component. The solution isthen stirred for a period of time of about 2 to about 10 hours at roomtemperature or slightly elevated up to 40° C.

In another example, the silane coupling reaction can be performed byhydrolytic deposition of silanes (B. Arkles, CHEMTECH, 7, 766, 1977)where the silane oligomers hydrogen bond with OH groups of thesubstrate. During drying or curing, a covalent linkage is formed withthe substrate with concomitant loss of water. Methods for enhancingreactivity include transesterification catalysts and agents whichincrease the acidity of hydroxyl groups on the substrate by hydrogenbonding. Transesterification catalysts include tin compounds such asdibutyldiacetoxytin and titanates such as titanium isopropoxide.Incorporation of transesterification catalysts at about 2 wt % to about3 wt % of the silane effectively promotes reaction and deposition inmany instances, others include tetrabutyl titanate or the reaction canbe promoted by addition of catalytic amounts of amines such asbenzyldimethylamine The reaction conditions may include a coupling agentmay be present at about 0.1 wt % to about 5 wt % relative to thepigment, reaction times may be about 4 hours to about 12 hours,temperatures may be about 50° C. to about 120° C., and ethanol solventmay be preferred over methanol, where water in the solvent is at levelsof about 1 wt % to about 5 wt % to promote hydrolysis of the silaneduring attachment to the surface.

In yet another example, the silane coupling reaction can be performed byanhydrous liquid phase deposition where toluene, tetrahydrofuran, and/orhydrocarbon solutions are prepared containing about 1 wt % to about 10wt % silane. The mixture is refluxed for about 12 hours to about 24hours with the substrate (pigment in this instance) to be treated. Thetreated pigment is washed with the solvent. The solvent is then removedby air or explosion proof oven drying. No further cure is necessary.

The epoxide group on the metallic pigment reactions with the polyamidemay be performed under an atmosphere (nitrogen or argon) at temperaturesof about 70° C. to about 200° C. (or about 70° C. to about 150° C., orabout 125° C. to about 200° C.) in the presence of an organic solventsuch as tetrahydrofuan, dimethylformamide or toluene or the like. Themixture is then stirred for about 24 hours at an elevated temperature.After cooling the mixture to room temperature, the grafted polymer isfiltered and washed to remove organic impurities and unreacted startingreagents.

Scheme 2 below is a second nonlimiting example synthesis of aPP-polyamide. More specifically, silica particles having a surfacefunctionality with at least one carboxylic acid (which may be terminalas shown, pendent, or both terminal and pendent) are grafted onto themetal oxide particle (but some may graft to the pigment depending on thepigment compositions). Then, the carboxylic acids from thefunctionalized silica particles are converted to acid chlorides, whichreact with the nitrogen of the amide in the polyamide (illustrated usingnylon 6) to yield a PP-polyamide. As illustrated, the pigment ischemically linked to four polyamide chains, which illustrates that thesurface coated pigment (surface of the pigment and/or surface of themetal oxide particles) may also be a crosslinker.

Examples of functionalized silica particles include, but are not limitedto, 3-aminopropyl-(3-oxobutanoic) acid functionalized silica,3-propylsulphonic acid-functionalized silica gel, propylcarboxylic acidfunctionalized silica, triaminetetraacetic acid-functionalized silicagel, propionyl chloride-functionalized silica gel, 3-carboxypropylfunctionalized silica gel, aminomethylphosphonic acid(AMPA)-functionalized silica gel,1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid(DOTA)-functionalized silica gel, and the like, and any combinationthereof.

The grafting reaction of the functionalized silica to the pigment can beperformed by known methods. Similar to the glycidyl functionalizedcoated pigments of Scheme 1, silanes that contain reactive alkoxy (OR)functional groups can react with the surface hydroxyl groups of themetal oxide particles and/or the pigments. When the silane solution isapplied onto the surface hydroxyl groups of the metal oxide particlesand/or the pigments, the free silanol groups first form hydrogen bondingwith the hydroxyl (—OH) groups on the metal oxide particles and/or thepigments at ambient temperature. Then, a SiO₂ linkage is formed betweenthe silanol and the —OH groups on the surface of the SiO₂ linkage bycondensation.

The conversion of the carboxylic acid to the more reactive acid chloridecan be performed by known methods. For example, oxalyl chloride (COCl)₂and/or thionyl chloride SOCl₂ may be used as chlorinating agents inconjunction with a catalyst. Solvents for said reactions may include,but are not limited to, dimethylformamide, dichloromethane, and thelike, and any combination thereof.

The acid chloride/polyamide reaction with the polyamide may be performedby known methods. For example, the pigment having the acid chloridefunctionality may be melt mixed with polyamide at about 125° C. to about250° C. (or about 125° C. to about 200° C., or about 150° C. to about225° C., or about 200° C. to about 250° C.) for about 15 minutes toabout 1 hour or longer (or about 15 minutes to about 30 minutes, orabout 20 minutes to about 40 minutes, or about 30 minutes to about 1hour).

Scheme 1 and Scheme 2 include nonlimiting examples of synthetic routesto producing a surface treated pigment having pendent epoxy orcarboxylic acid moieties. Other reaction schemes will be apparent tothose skilled in the art.

The surface treated pigment having pendent epoxy or carboxylic acidmoieties are reacted with the polyamide to yield the PP-polyamidesdescribed herein.

Whether by Scheme 1, Scheme 2, or another coupling reaction scheme, thePP-polyamides described herein may have a weight ratio of pigment topolyamide of about 1:10 to about 1:1000 (or about 1:10 to about 1:200,or about 1:100 to about 1:500, or about 1:250 to about 1:1000).

Applications of PP-Polyamides

The PP-polyamides described herein may be used to produce a variety ofobjects (or articles). The PP-polyamides described herein may be usedalone or in combination with other thermoplastic polymers (e.g.,polyamides without an optical absorber and/or other thermoplasticpolymers). Examples of thermoplastic polymers that may be used inconjunction with one or more PP-polyamides of the present disclosureinclude, but are not limited to, polyamides (e.g., polyamides notcoupled to a pigment), polyurethanes, polyethylenes, polypropylenes,polyacetals, polycarbonates, polybutylene terephthalate (PBT),polyethylene terephthalate (PET), polyethylene naphthalate (PEN),polytrimethylene terephthalate (PTT), polyhexamethylene terephthalate,polystyrenes, polyvinyl chlorides, polytetrafluoroethenes, polyesters(e.g., polylactic acid), polyethers, polyether sulfones, polyetheretherketones, polyacrylates, polymethacrylates, polyimides, acrylonitrilebutadiene styrene (ABS), polyphenylene sulfides, vinyl polymers,polyarylene ethers, polyarylene sulfides, polysulfones, polyetherketones, polyamide-imides, polyetherimides, polyetheresters, copolymerscomprising a polyether block and a polyamide block (PEBA or polyetherblock amide), grafted or ungrafted thermoplastic polyolefins,functionalized or nonfunctionalized ethylene/vinyl monomer polymer,functionalized or nonfunctionalized ethylene/alkyl (meth)acrylates,functionalized or nonfunctionalized (meth)acrylic acid polymers,functionalized or nonfunctionalized ethylene/vinyl monomer/alkyl(meth)acrylate terpolymers, ethylene/vinyl monomer/carbonyl terpolymers,ethylene/alkyl (meth)acrylate/carbonyl terpolymers,methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, chlorinated or chlorosulphonated polyethylenes,polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene/vinylacetate)s, polybutadienes, polyisoprenes, styrenic block copolymers,polyacrylonitriles, silicones, and the like, and any combinationthereof. Copolymers comprising one or more of the foregoing may also beused in the methods and systems described herein.

If needed, compatibilizers may be used when combining the PP-polyamidesdescribed herein with other thermoplastic polymers. Compatibilizers mayimprove the blending efficiency and/or efficacy of the polymers.Examples of polymer compatibilizers include, but are not limited to,PROPOLDER™ MPP2020 20 (polypropylene, available from Polygroup Inc.),PROPOLDER™ MPP2040 40 (polypropylene, available from Polygroup Inc.),NOVACOM™ HFS2100 (maleic anhydride functionalized high densitypolyethylene polymer, available from Polygroup Inc.), KEN-REACT™ CAPS™L™ 12/L (organometallic coupling agent, available from KenrichPetrochemicals), KEN-REACT™ CAPOW™ L™ 12/H (organometallic couplingagent, available from Kenrich Petrochemicals), KEN-REACT™ LICA™ 12(organometallic coupling agent, available from Kenrich Petrochemicals),KEN-REACT™ CAPS™ KPR™ 12/LV (organometallic coupling agent, availablefrom Kenrich Petrochemicals), KEN-REACT™ CAPOW™ KPR™ 12/H(organometallic coupling agent, available from Kenrich Petrochemicals),KEN-REACT™ titanates & zirconates (organometallic coupling agent,available from Kenrich Petrochemicals), VISTAMAXX™ (ethylene-propylenecopolymers, available from ExxonMobil), SANTOPRENE™ (thermoplasticvulcanizate of ethylene-propylene-diene rubber and polypropylene,available from ExxonMobil), VISTALON™ (ethylene-propylene-diene rubber,available from ExxonMobil), EXACT™ (plastomers, available fromExxonMobil) EXXELOR™ (polymer resin, available from ExxonMobil),FUSABOND™ M603 (random ethylene copolymer, available from Dow),FUSABOND™ E226 (anhydride modified polyethylene, available from Dow),BYNEL™ 41E710 (coextrudable adhesive resin, available from Dow), SURLYN™1650 (ionomer resin, available from Dow), FUSABOND™ P353 (a chemicallymodified polypropylene copolymer, available from Dow), ELVALOY™ PTW(ethylene terpolymer, available from Dow), ELVALOY™ 3427AC (a copolymerof ethylene and butyl acrylate, available from Dow), LOTADER™ AX8840(ethylene acrylate-based terpolymer, available from Arkema), LOTADER™3210 (ethylene acrylate-based terpolymer, available from Arkema),LOTADER™ 3410 (ethylene acrylate-based terpolymer, available fromArkema), LOTADER™ 3430 (ethylene acrylate-based terpolymer, availablefrom Arkema), LOTADER™ 4700 (ethylene acrylate-based terpolymer,available from Arkema), LOTADER™ AX8900 (ethylene acrylate-basedterpolymer, available from Arkema), LOTADER™ 4720 (ethyleneacrylate-based terpolymer, available from Arkema), BAXXODUR™ EC 301(amine for epoxy, available from BASF), BAXXODUR™ EC 311 (amine forepoxy, available from BASF), BAXXODUR™ EC 303 (amine for epoxy,available from BASF), BAXXODUR™ EC 280 (amine for epoxy, available fromBASF), BAXXODUR™ EC 201 (amine for epoxy, available from BASF),BAXXODUR™ EC 130 (amine for epoxy, available from BASF), BAXXODUR™ EC110 (amine for epoxy, available from BASF), styrenics, polypropylene,polyamides, polycarbonate, EASTMAN™ G-3003 (a maleic anhydride graftedpolypropylene, available from Eastman), RETAIN™ (polymer modifieravailable from Dow), AMPLIFY TY™ (maleic anhydride grafted polymer,available from Dow), INTUNE™ (olefin block copolymer, available fromDow), and the like and any combination thereof.

Methods for producing objects include, but are not limited to, meltextrusion, injection molding, compression molding, melt spinning, meltemulsification, spray drying (e.g., to form particles), cryogenicmilling (or cryogenic grinding), freeze drying polymer dispersions,precipitation of polymer dispersions, and the like, and any hybridthereof.

Examples of articles that may be produced by such methods where thePP-polyimide may be all or a portion of said articles include, but arenot limited to, particles, films, packaging, toys, household goods,automotive parts, aerospace/aircraft-related parts, containers (e.g.,for food, beverages, cosmetics, personal care compositions, medicine,and the like), shoe soles, furniture parts, decorative home goods,plastic gears, screws, nuts, bolts, cable ties, jewelry, art, sculpture,medical items, prosthetics, orthopedic implants, production of artifactsthat aid learning in education, 3D anatomy models to aid in surgeries,robotics, biomedical devices (orthotics), home appliances, dentistry,electronics, sporting goods, and the like. Further, particles may beuseful in applications that include, but are not limited to, paints,powder coatings, ink jet materials, electrophotographic toners, 3Dprinting, and the like.

In addition, the PP-polyamides described herein may have a specificchemical fingerprint that is useful in identifying objects, trackingobjects, authenticating objects, and/or determining the health ofobjects. Further, the placement of where the PP-polyamides are locatedin the objects is another layer of fingerprinting the objects foridentifying objects, tracking objects, authenticating objects, and/ordetermining the health of objects.

Methods of identifying objects, tracking objects, authenticatingobjects, and/or determining the health of objects may include (a)exposing the object comprising PP-polyamides to electromagneticradiation; (b) sensing one or more spectra related to theelectromagnetic radiation absorbed and/or reemitted; and (c) comparingthe spectra to the known spectra for the optical absorbers used in saidobject or portion thereof. Optionally, the location of where the spectraarea is located on the object may be compared to the known locationwhere the spectra area should be. The comparison(s) can be used foridentifying and/or authenticating the object. For tracking, thecomparison(s) may be done and/or the detected spectra and/or spectraarea may be logged into a database along with the physical location ofthe object. Further, the health of objects that wear and/or crack can beascertained. For example, a core portion of the article may compriseoptical absorbers and an outer portion may cover the core portion andnot comprise the optical absorbers (or comprise different opticalabsorbers). Then, when comparing spectra, the appearance of spectralfeatures for the optical absorbers in the core may indicate that theobject is at or near the end of life.

By way of nonlimiting example, 3-D printing processes of the presentdisclosure may comprise: depositing particles comprising one or morePP-polyamides of the present disclosure (and optionally one or moreother thermoplastic polymers and/or one or more compatibilizers) upon asurface in a specified shape, and once deposited, heating at least aportion of the particles to promote consolidation thereof and form aconsolidated body (object), such that the consolidated body has a voidpercentage of about 1% or less after being consolidated. For example,heating and consolidation of the thermoplastic polymer particles maytake place in a 3-D printing apparatus employing a laser, such thatheating and consolidation take place by selective laser sintering.

By way of nonlimiting example, 3-D printing processes of the presentdisclosure may comprise: extruding a filament comprising one or morePP-polyamides of the present disclosure (and optionally one or moreother thermoplastic polymers and/or one or more compatibilizers) throughan orifice, wherein the filament becomes a polymer melt upon extrusion;depositing the polymer melt as a first layer on a platform; cooling thelayer; depositing an additional layer of the polymer melt on the firstlayer; cooling the additional layer; repeating depositing and coolingfor at least one additional layer to produce a 3-D shape.

Yet another nonlimiting example is a method comprising: extruding apolymer melt comprising one or more PP-polyamides of the presentdisclosure (and optionally one or more other thermoplastic polymersand/or one or more compatibilizers) through an orifice to produce afilm, a fiber (or a filament), particles, pellets, or the like.

Thermoplastic Polymer Particles and Methods of Making

The FIG. 1 s a flow chart of a nonlimiting example method 100 of thepresent disclosure. Thermoplastic polymer 102 (comprising one or morePP-polyamides and optionally one or more other thermoplastic polymers),carrier fluid 104, and optionally emulsion stabilizer 106 are combined108 to produce a mixture 110. The components 102, 104, and 106 can beadded in any order and include mixing and/or heating during the processof combining 108 the components 102, 104, and 106.

The mixture 110 is then processed 112 by applying sufficiently highshear to the mixture 110 at a temperature greater than the melting pointor softening temperature of the thermoplastic polymer 102 to form a meltemulsion 114. Because the temperature is above the melting point orsoftening temperature of the thermoplastic polymer 102, thethermoplastic polymer 102 becomes a polymer melt. The shear rate shouldbe sufficient enough to disperse the polymer melt in the carrier fluid104 as droplets (i.e., the polymer emulsion 114). Without being limitedby theory, it is believed that, all other factors being the same,increasing shear should decrease the size of the droplets of the polymermelt in the carrier fluid 104. However, at some point there may bediminishing returns on increasing shear and decreasing droplet size ormay be disruptions to the droplet contents that decrease the quality ofparticles produced therefrom.

The melt emulsion 114 inside and/or outside the mixing vessel is thencooled 116 to solidify the polymer droplets into thermoplastic polymerparticles (also referred to as solidified thermoplastic polymerparticles). The cooled mixture 118 can then be treated 120 to isolatethe thermoplastic polymer particles 122 from other components 124 (e.g.,the carrier fluid 104, excess emulsion stabilizer 106, and the like) andwash or otherwise purify the thermoplastic polymer particles 122. Thethermoplastic polymer particles 122 comprise the thermoplastic polymer102 and, when included, at least a portion of the emulsion stabilizer106 coating the outer surface of the thermoplastic polymer particles122. Emulsion stabilizers 106, or a portion thereof, may be deposited asa uniform coating on the thermoplastic polymer particles 122. In someinstances, which may be dependent upon non-limiting factors such as thetemperature (including cooling rate), the type of thermoplastic polymer102, and the types and sizes of emulsion stabilizers 106, thenanoparticles of emulsion stabilizers 106 may become at least partiallyembedded within the outer surface of the thermoplastic polymer particles122 in the course of becoming associated therewith. Even withoutembedment taking place, at least the nanoparticles within emulsionstabilizers 106 may remain robustly associated with thermoplasticpolymer particles 122 to facilitate their further use. In contrast, dryblending already formed thermoplastic polymer particulates (e.g., formedby cryogenic grinding or precipitation processes) with a flow aid likesilica nanoparticles does not result in a robust, uniform coating of theflow aid upon the thermoplastic polymer particulates.

Advantageously, carrier fluids and washing solvents of the systems andmethods described herein (e.g., method 100) can be recycled and reused.One skilled in the art will recognize any necessary cleaning of usedcarrier fluid and solvent necessary in the recycling process.

The thermoplastic polymer 102 and carrier fluid 104 should be chosensuch that at the various processing temperatures (e.g., from roomtemperature to process temperature) the thermoplastic polymer 102 andcarrier fluid 104 are immiscible. An additional factor that may beconsidered is the differences in (e.g., a difference or a ratio of)viscosity at process temperature between the molten polyamide 102 andthe carrier fluid 104. The differences in viscosity may affect dropletbreakup and particle size distribution. Without being limited by theory,it is believed that when the viscosities of the molten polyamide 102 andthe carrier fluid 104 are too similar, the circularity of the product asa whole may be reduced where the particles are more ovular and moreelongated structures are observed.

The thermoplastic polymers 102 comprises one or more PP-polyamides andoptionally one or more other thermoplastic polymers. Examples of otherthermoplastic polymers include, but are not limited to, polyamides,polyurethanes, polyethylenes, polypropylenes, polyacetals,polycarbonates, polybutylene terephthalate (PBT), polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), polytrimethyleneterephthalate (PTT), polyhexamethylene terephthalate, polystyrenes,polyvinyl chlorides, polytetrafluoroethenes, polyesters (e.g.,polylactic acid), polyethers, polyether sulfones, polyetheretherketones, polyacrylates, polymethacrylates, polyimides, acrylonitrilebutadiene styrene (ABS), polyphenylene sulfides, vinyl polymers,polyarylene ethers, polyarylene sulfides, polysulfones, polyetherketones, polyamide-imides, polyetherimides, polyetheresters, copolymerscomprising a polyether block and a polyamide block (PEBA or polyetherblock amide), grafted or ungrafted thermoplastic polyolefins,functionalized or nonfunctionalized ethylene/vinyl monomer polymer,functionalized or nonfunctionalized ethylene/alkyl (meth)acrylates,functionalized or nonfunctionalized (meth)acrylic acid polymers,functionalized or nonfunctionalized ethylene/vinyl monomer/alkyl(meth)acrylate terpolymers, ethylene/vinyl monomer/carbonyl terpolymers,ethylene/alkyl (meth)acrylate/carbonyl terpolymers,methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, chlorinated or chlorosulphonated polyethylenes,polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene/vinylacetate)s, polybutadienes, polyisoprenes, styrenic block copolymers,polyacrylonitriles, silicones, and the like, and any combinationthereof. Copolymers comprising one or more of the foregoing may also beused in the methods and systems of the present disclosure.

The other thermoplastic polymers in the compositions and methods of thepresent disclosure may be elastomeric or non-elastomeric. Some of theforegoing examples of other thermoplastic polymers may be elastomeric ornon-elastomeric depending on the exact composition of the polymer. Forexample, polyethylene that is a copolymer of ethylene and propylene maybe elastomeric or not depending on the amount of propylene in thepolymer.

Thermoplastic elastomers generally fall within one of six classes:styrenic block copolymers, thermoplastic polyolefin elastomers,thermoplastic vulcanizates (also referred to as elastomeric alloys),thermoplastic polyurethanes, thermoplastic copolyesters, andthermoplastic polyamides (typically block copolymers comprisingpolyamide). Examples of thermoplastic elastomers can be found in theHandbook of Thermoplastic Elastomers, 2nd ed., B. M. Walker and C. P.Rader, eds., Van Nostrand Reinhold, New York, 1988. Examples ofthermoplastic elastomers include, but are not limited to, elastomericpolyamides, polyurethanes, copolymers comprising a polyether block and apolyamide block (PEBA or polyether block amide), methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, polybutadienes, polyisoprenes, styrenic blockcopolymers, and polyacrylonitriles), silicones, and the like.Elastomeric styrenic block copolymers may include at least one blockselected from the group of: isoprene, isobutylene, butylene,ethylene/butylene, ethylene-propylene, and ethylene-ethylene/propylene.More specific elastomeric styrenic block copolymer examples include, butare not limited to, poly(styrene-ethylene/butylene),poly(styrene-ethylene/butylene-styrene),poly(styrene-ethylene/propylene), styrene-ethylene/propylene-styrene),poly(styrene-ethylene/propylene-styrene-ethylene-propylene),poly(styrene-butadiene-styrene),poly(styrene-butylene-butadiene-styrene), and the like, and anycombination thereof.

Examples of polyamides include, but are not limited to, those describedabove. Examples of polyamide elastomers include, but are not limited to,polyesteramide, polyetheresteramide, polycarbonate-esteramide, andpolyether-block-amide elastomers.

Examples of polyurethanes include, but are not limited to, polyetherpolyurethanes, polyester polyurethanes, mixed polyether and polyesterpolyurethanes, and the like, and any combination thereof. Examples ofthermoplastic polyurethanes include, but are not limited to,poly[4,4′-methylenebis(phenylisocyanate)-alt-1,4-butanediol/di(propyleneglycol)/polycaprolactone], ELASTOLLAN® 1190A (a polyether polyurethaneelastomer, available from BASF), ELASTOLLAN® 1190A10 (a polyetherpolyurethane elastomer, available from BASF), and the like, and anycombination thereof.

Compatibilizers may optionally be used to improve the blendingefficiency and efficacy of PP-polyamides with one or more thermoplasticpolymers. Examples of polymer compatibilizers include, but are notlimited to, the compatibilizers described above.

The thermoplastic polymers 102 (comprising one or more PP-polyamides andoptionally one or more other thermoplastic polymers) may have a meltingpoint or softening temperature of about 50° C. to about 450° C. (orabout 50° C. to about 125° C., or about 100° C. to about 175° C., orabout 150° C. to about 280° C., or about 200° C. to about 350° C., orabout 300° C. to about 450° C.).

The thermoplastic polymers 102 may have a glass transition temperature(ASTM E1356-08(2014) with 10° C./min ramping and cooling rates) of about−50° C. to about 400° C. (or about −50° C. to about 0° C., or about −25°C. to about 50° C., or about 0° C. to about 150° C., or about 100° C. toabout 250° C., or about 150° C. to about 300° C., or about 200° C. toabout 400° C.).

The thermoplastic polymers 102 may optionally comprise an additive.Typically, the additive would be present before addition of thethermoplastic polymers 102 to the mixture 110. Therefore, in thethermoplastic polymer melt droplets and resultant thermoplastic polymerparticles, the additive is dispersed throughout the thermoplasticpolymer. Accordingly, for clarity, this additive is referred to hereinas an “internal additive.” The internal additive may be blended with thethermoplastic polymer just prior to making the mixture 110 or well inadvance.

When describing component amounts in the compositions described herein(e.g., the mixture 110 and the thermoplastic polymer particles 122), aweight percent based on the thermoplastic polymer 102 not inclusive ofthe internal additive. For example, a composition comprising 1 wt % ofemulsion stabilizer by weight of 100 g of a thermoplastic polymer 102comprising 10 wt % internal additive and 90 wt % thermoplastic polymeris a composition comprising 0.9 g of emulsion stabilizer, 90 g ofthermoplastic polymer, and 10 g of internal additive.

The internal additive may be present in the thermoplastic polymer 102 atabout 0.1 wt % to about 60 wt % (or about 0.1 wt % to about 5 wt %, orabout 1 wt % to about 10 wt %, or about 5 wt % to about 20 wt %, orabout 10 wt % to about 30 wt %, or about 25 wt % to about 50 wt %, orabout 40 wt % to about 60 wt %) of the thermoplastic polymer 102. Forexample, the thermoplastic polymer 102 may comprise about 70 wt % toabout 85 wt % of a thermoplastic polymer and about 15 wt % to about 30wt % of an internal additive like glass fiber or carbon fiber.

Examples of internal additives include, but are not limited to, fillers,strengtheners, pigments, pH regulators, and the like, and combinationsthereof. Examples of fillers include, but are not limited to, glassfibers, glass particles, mineral fibers, carbon fiber, oxide particles(e.g., titanium dioxide and zirconium dioxide), metal particles (e.g.,aluminum powder), and the like, and any combination thereof. Examples ofpigments include, but are not limited to, organic pigments, inorganicpigments, carbon black, and the like, and any combination thereof.

The thermoplastic polymer 102 may be present in the mixture 110 at about5 wt % to about 60 wt % (or about 5 wt % to about 25 wt %, or about 10wt % to about 30 wt %, or about 20 wt % to about 45 wt %, or about 25 wt% to about 50 wt %, or about 40 wt % to about 60 wt %) of thethermoplastic polymer 102 and carrier fluid 104 combined.

Suitable carrier fluids 104 have a viscosity at 25° C. of about 1000 cStto about 150,000 cSt (or about 1000 cSt to about 60,000 cSt, or about40,000 cSt to about 100,000 cSt, or about 75,000 cSt to about 150,000cSt).

Examples of carrier fluids 104 include, but are not limited to, siliconeoil, fluorinated silicone oils, perfluorinated silicone oils,polyethylene glycols, alkyl-terminal polyethylene glycols (e.g., C1-C4terminal alkyl groups like tetraethylene glycol dimethyl ether (TDG)),paraffins, liquid petroleum jelly, vison oils, turtle oils, soya beanoils, perhydrosqualene, sweet almond oils, calophyllum oils, palm oils,parleam oils, grapeseed oils, sesame oils, maize oils, rapeseed oils,sunflower oils, cottonseed oils, apricot oils, castor oils, avocadooils, jojoba oils, olive oils, cereal germ oils, esters of lanolic acid,esters of oleic acid, esters of lauric acid, esters of stearic acid,fatty esters, higher fatty acids, fatty alcohols, polysiloxanes modifiedwith fatty acids, polysiloxanes modified with fatty alcohols,polysiloxanes modified with polyoxy alkylenes, and the like, and anycombination thereof. Examples of silicone oils include, but are notlimited to, polydimethylsiloxane, methylphenylpolysiloxane, an alkylmodified polydimethylsiloxane, an alkyl modifiedmethylphenylpolysiloxane, an amino modified polydimethylsiloxane, anamino modified methylphenylpolysiloxane, a fluorine modifiedpolydimethylsiloxane, a fluorine modified methylphenylpolysiloxane, apolyether modified polydimethylsiloxane, a polyether modifiedmethylphenylpolysiloxane, and the like, and any combination thereof. Thecarrier fluid 104 may have one or more phases. For example,polysiloxanes modified with fatty acids and polysiloxanes modified withfatty alcohols (preferably with similar chain lengths for the fattyacids and fatty alcohols) may form a single-phase carrier fluid 104. Inanother example, a carrier fluid 104 comprising a silicone oil and analkyl-terminal polyethylene glycol may form a two-phase carrier fluid104.

The carrier fluid 104 may be present in the mixture 110 at about 40 wt %to about 95 wt % (or about 75 wt % to about 95 wt %, or about 70 wt % toabout 90 wt %, or about 55 wt % to about 80 wt %, or about 50 wt % toabout 75 wt %, or about 40 wt % to about 60 wt %) of the thermoplasticpolymer 102 and carrier fluid 104 combined.

In some instances, the carrier fluid 104 may have a density of about 0.6g/cm³ to about 1.5 g/cm³, and the thermoplastic polymer 102 has adensity of about 0.7 g/cm³ to about 1.7 g/cm³, wherein the thermoplasticpolymer has a density similar, lower, or higher than the density of thecarrier fluid.

The emulsion stabilizers used in the methods and compositions of thepresent disclosure may comprise nanoparticles (e.g. oxide nanoparticles,carbon black, polymer nanoparticles, and combinations thereof),surfactants, and the like, and any combination thereof.

Oxide nanoparticles may be metal oxide nanoparticles, non-metal oxidenanoparticles, or mixtures thereof. Examples of oxide nanoparticlesinclude, but are not limited to, silica, titania, zirconia, alumina,iron oxide, copper oxide, tin oxide, boron oxide, cerium oxide, thalliumoxide, tungsten oxide, and the like, and any combination thereof. Mixedmetal oxides and/or non-metal oxides, like aluminosilicates,borosilicates, and aluminoborosilicates, are also inclusive in the termmetal oxide. The oxide nanoparticles may by hydrophilic or hydrophobic,which may be native to the particle or a result of surface treatment ofthe particle. For example, a silica nanoparticle having a hydrophobicsurface treatment, like dimethyl silyl, trimethyl silyl, and the like,may be used in methods and compositions of the present disclosure.Additionally, silica with functional surface treatments likemethacrylate functionalities may be used in methods and compositions ofthe present disclosure. Unfunctionalized oxide nanoparticles may also besuitable for use as well.

Commercially available examples of silica nanoparticles include, but arenot limited to, AEROSIL® particles available from Evonik (e.g., AEROSIL®R812S (about 7 nm average diameter silica nanoparticles having ahydrophobically modified surface and a BET surface area of 260±30 m²/g),AEROSIL® RX50 (about 40 nm average diameter silica nanoparticles havinga hydrophobically modified surface and a BET surface area of 35±10m²/g), AEROSIL® 380 (silica nanoparticles having a hydrophilicallymodified surface and a BET surface area of 380±30 m²/g)), and the like,and any combination thereof.

Carbon black is another type of nanoparticle that may be present as anemulsion stabilizer in the compositions and methods disclosed herein.Various grades of carbon black will be familiar to one having ordinaryskill in the art, any of which may be used herein. Other nanoparticlescapable of absorbing infrared radiation may be used similarly.

Polymer nanoparticles are another type of nanoparticle that may bepresent as an emulsion stabilizer in the disclosure herein. Suitablepolymer nanoparticles may include one or more polymers that arethermosetting and/or crosslinked, such that they do not melt whenprocessed by melt emulsification according to the disclosure herein.High molecular weight thermoplastic polymers having high melting ordecomposition points may similarly comprise suitable polymernanoparticle emulsion stabilizers.

The nanoparticles may have an average diameter (D50 based on volume) ofabout 1 nm to about 500 nm (or about 10 nm to about 150 nm, or about 25nm to about 100 nm, or about 100 nm to about 250 nm, or about 250 nm toabout 500 nm).

The nanoparticles may have a BET surface area of about 10 m²/g to about500 m²/g (or about 10 m²/g to about 150 m²/g, or about 25 m²/g to about100 m²/g, or about 100 m²/g to about 250 m²/g, or about 250 m²/g toabout 500 m²/g).

Nanoparticles may be included in the mixture 110 at a concentration ofabout 0.01 wt % to about 10 wt % (or about 0.01 wt % to about 1 wt %, orabout 0.1 wt % to about 3 wt %, or about 1 wt % to about 5 wt %, orabout 5 wt % to about 10 wt %) based on the weight of the thermoplasticpolymer 102.

Surfactants may be anionic, cationic, nonionic, or zwitterionic.Examples of surfactants include, but are not limited to, sodium dodecylsulfate, sorbitan oleates,poly[dimethylsiloxane-co-[3-(2-(2-hydroxyethoxy)ethoxy)propylmethylsiloxane],docusate sodium (sodium1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate), and the like, andany combination thereof. Commercially available examples of surfactantsinclude, but are not limited to, CALFAX® DB-45 (sodium dodecyl diphenyloxide disulfonate, available from Pilot Chemicals), SPAN® 80 (sorbitanmaleate non-ionic surfactant), MERPOL® surfactants (available fromStepan Company), TERGITOL™ TMN-6 (a water-soluble, nonionic surfactant,available from DOW), TRITON™ X-100 (octyl phenol ethoxylate, availablefrom SigmaAldrich), IGEPAL® CA-520 (polyoxyethylene (5) isooctylphenylether, available from SigmaAldrich), BRIJ® S10 (polyethylene glycoloctadecyl ether, available from SigmaAldrich), and the like, and anycombination thereof.

Surfactants may be included in the mixture 110 at a concentration ofabout 0.01 wt % to about 10 wt % (or about 0.01 wt % to about 1 wt %, orabout 0.5 wt % to about 2 wt %, or about 1 wt % to about 3 wt %, orabout 2 wt % to about 5 wt %, or about 5 wt % to about 10 wt %) based onthe weight of the polyamide 102. Alternatively, the mixture 110 maycomprise no (or be absent of) surfactant.

A weight ratio of nanoparticles to surfactant may be about 1:10 to about10:1 (or about 1:10 to about 1:1, or about 1:5 to about 5:1, or about1:1 to about 10:1).

As described above, the components 102, 104, and 106 can be added in anyorder and include mixing and/or heating during the process of combining108 the components 102, 104, and 106. For example, the emulsionstabilizer 106 may first be dispersed in the carrier fluid 104,optionally with heating said dispersion, before adding the thermoplasticpolymer 102. In another nonlimiting example, the thermoplastic polymer102 may be heated to produce a polymer melt to which the carrier fluid104 and emulsion stabilizer 106 are added together or in either order.In yet another nonlimiting example, the thermoplastic polymer 102 andcarrier fluid 104 can be mixed at a temperature greater than the meltingpoint or softening temperature of the thermoplastic polymer 102 and at ashear rate sufficient enough to disperse the thermoplastic polymer meltin the carrier fluid 104. Then, the emulsion stabilizer 106 can be addedto form the mixture 110 and maintained at suitable process conditionsfor a set period of time.

Combining 108 the components 102, 104, and 106 in any combination canoccur in a mixing apparatus used for the processing 112 and/or anothersuitable vessel. By way of nonlimiting example, the thermoplasticpolymer 102 may be heated to a temperature greater than the meltingpoint or softening temperature of the thermoplastic polymer 102 in themixing apparatus used for the processing 112, and the emulsionstabilizer 106 may be dispersed in the carrier fluid 104 in anothervessel. Then, said dispersion may be added to the melt of thethermoplastic polymer 102 in the mixing apparatus used for theprocessing 112.

The mixing apparatuses used for the processing 112 to produce the meltemulsion 114 should be capable of maintaining the melt emulsion 114 at atemperature greater than the melting point or softening temperature ofthe thermoplastic polymer 102 and applying a shear rate sufficient todisperse the polymer melt in the carrier fluid 104 as droplets.

Examples of mixing apparatuses used for the processing 112 to producethe melt emulsion 114 include, but are not limited to, extruders (e.g.,continuous extruders, batch extruders, and the like), stirred reactors,blenders, reactors with inline homogenizer systems, and the like, andapparatuses derived therefrom.

Processing 112 and forming the melt emulsion 114 at suitable processconditions (e.g., temperature, shear rate, and the like) for a setperiod of time.

The temperature of processing 112 and forming the melt emulsion 114should be a temperature greater than the melting point or softeningtemperature of the thermoplastic polymer 102 and less than thedecomposition temperature of any components 102, 104, and 106 in themixture 110. For example, the temperature of processing 112 and formingthe melt emulsion 114 may be about 1° C. to about 50° C. (or about 1° C.to about 25° C., or about 5° C. to about 30° C., or about 20° C. toabout 50° C.) greater than the melting point or softening temperature ofthe thermoplastic polymer 102 provided the temperature of processing 112and forming the melt emulsion 114 is less than the decompositiontemperature of any components 102, 104, and 106 in the mixture 110.

The shear rate of processing 112 and forming the melt emulsion 114should be sufficiently high to disperse the polymer melt in the carrierfluid 104 as droplets. Said droplets should comprise droplets having adiameter of about 1000 μm or less (or about 1 μm to about 1000 μm, orabout 1 μm to about 50 μm, or about 10 μm to about 100 μm, or about 10μm to about 250 μm, or about 50 μm to about 500 μm, or about 250 μm toabout 750 μm, or about 500 μm to about 1000 μm).

The time for maintaining said temperature and shear rate for processing112 and forming the melt emulsion 114 may be 10 seconds to 18 hours orlonger (or 10 seconds to 30 minutes, or 5 minutes to 1 hour, or 15minutes to 2 hours, or 1 hour to 6 hours, or 3 hours to 18 hours).Without being limited by theory, it is believed that a steady state ofdroplet sizes will be reached at which point processing 112 can bestopped. That time may depend on, among other things, the temperature,shear rate, thermoplastic polymer 102 composition, the carrier fluid 104composition, and the emulsion stabilizer 106 composition.

The melt emulsion 114 may then be cooled 116. Cooling 116 can be slow(e.g., allowing the melt emulsion to cool under ambient conditions) tofast (e.g., quenching). For example, the rate of cooling may range fromabout 10° C./hour to about 100° C./second to almost instantaneous withquenching (for example in dry ice) (or about 10° C./hour to about 60°C./hour, or about 0.5° C./minute to about 20° C./minute, or about 1°C./minute to about 5° C./minute, or about 10° C./minute to about 60°C./minute, or about 0.5° C./second to about 10° C./second, or about 10°C./second to about 100° C./second).

During cooling, little to no shear may be applied to the melt emulsion114. In some instances, the shear applied during heating may be appliedduring cooling.

The cooled mixture 118 resulting from cooling 116 the melt emulsion 114comprises solidified thermoplastic polymer particles 122 (or simplythermoplastic polymer particles) and other components 124 (e.g., thecarrier fluid 104, excess emulsion stabilizer 106, and the like). Thethermoplastic polymer particles may be dispersed in the carrier fluid orsettled in the carrier fluid.

The cooled mixture 118 may then be treated 120 to the separatethermoplastic polymer particles 122 (or simply thermoplastic polymerparticles 122) from the other components 124. Suitable treatmentsinclude, but are not limited to, washing, filtering, centrifuging,decanting, and the like, and any combination thereof.

Solvents used for washing the thermoplastic polymer particles 122 shouldgenerally be (a) miscible with the carrier fluid 104 and (b) nonreactive(e.g., non-swelling and non-dissolving) with the thermoplastic polymer102. The choice of solvent will depend on, among other things, thecomposition of the carrier fluid and the composition of thethermoplastic polymer 102.

Examples of solvents include, but are not limited to, hydrocarbonsolvents (e.g., pentane, hexane, heptane, octane, cyclohexane,cyclopentane, decane, dodecane, tridecane, and tetradecane), aromatichydrocarbon solvents (e.g., benzene, toluene, xylene, 2-methylnaphthalene, and cresol), ether solvents (e.g., diethyl ether,tetrahydrofuran, diisopropyl ether, and dioxane), ketone solvents (e.g.,acetone and methyl ethyl ketone), alcohol solvents (e.g., methanol,ethanol, isopropanol, and n-propanol), ester solvents (e.g., ethylacetate, methyl acetate, butyl acetate, butyl propionate, and butylbutyrate), halogenated solvents (e.g., chloroform, bromoform,1,2-dichloromethane, 1,2-dichloroethane, carbon tetrachloride,chlorobenzene, and hexafluoroisopropanol), water, and the like, and anycombination thereof.

Solvent may be removed from the thermoplastic polymer particles 122 bydrying using an appropriate method such as air-drying, heat-drying,reduced pressure drying, freeze drying, or a hybrid thereof. The heatingmay be performed preferably at a temperature lower than the glasstransition point of the thermoplastic polymer (e.g., about 50° C. toabout 150° C.).

The thermoplastic polymer particles 122 after separation from the othercomponents 124 may optionally be further classified to produce purifiedthermoplastic polymer particles 128. For example, to narrow the particlesize distribution (or reduce the diameter span), the thermoplasticpolymer particles 122 can be passed through a sieve having a pore sizeof about 10 μm to about 250 μm (or about 10 μm to about 100 μm, or about50 μm to about 200 μm, or about 150 μm to about 250 μm).

In another example purification technique, the thermoplastic polymerparticles 122 may be washed with water to remove surfactant whilemaintaining substantially all of the nanoparticles associated with thesurface of the thermoplastic polymer particles 122. In yet anotherexample purification technique, the thermoplastic polymer particles 122may be blended with additives to achieve a desired final product. Forclarity, because such additives are blended with the thermoplasticparticles 122 or other particles resultant from the methods describedherein after the particles are solidified, such additives are referredto herein as “external additives.” Examples of external additivesinclude flow aids, other polymer particles, fillers, and the like, andany combination thereof.

In some instances, a surfactant used in making the thermoplastic polymerparticles 122 may be unwanted in downstream applications. Accordingly,yet another example purification technique may include at leastsubstantial removal of the surfactant from the thermoplastic polymerparticles 122 (e.g., by washing and/or pyrolysis).

The thermoplastic polymer particles 122 and/or purified thermoplasticpolymer particles 128 (referred to as particles 122/128) may becharacterized by composition, physical structure, and the like.

As described above, the emulsion stabilizers are at the interfacebetween the polymer melt and the carrier fluid. As a result, when themixture is cooled, the emulsion stabilizers remain at, or in thevicinity of, said interface. Therefore, the structure of the particles122/128, in general, includes emulsion stabilizers (a) dispersed on anouter surface of the particles 122/128 and/or (b) embedded in an outerportion (e.g., outer 1 vol %) of the particles 122/128.

Further, where voids form inside the polymer melt droplets, emulsionstabilizers 106 should generally be at (and/or embedded in) theinterface between the interior of the void and the thermoplasticpolymer. The voids generally do not contain the thermoplastic polymer.Rather, the voids may contain, for example, carrier fluid, air, or bevoid. The particles 122/128 may comprise carrier fluid at about 5 wt %or less (or about 0.001 wt % to about 5 wt %, or about 0.001 wt % toabout 0.1 wt %, or about 0.01 wt % to about 0.5 wt %, or about 0.1 wt %to about 2 wt %, or about 1 wt % to about 5 wt %) of the particles122/128.

The thermoplastic polymer 102 may be present in the particles 122/128 atabout 90 wt % to about 99.5 wt % (or about 90 wt % to about 95 wt %, orabout 92 wt % to about 97 wt %, or about 95 wt % to about 99.5 wt %) ofthe particles 122/128.

When included, the emulsion stabilizers 106 may be present in theparticles 122/128 at about 10 wt % or less (or about 0.01 wt % to about10 wt %, or about 0.01 wt % to about 1 wt %, or about 0.5 wt % to about5 wt %, or about 3 wt % to about 7 wt %, or about 5 wt % to about 10 wt%) of the particles 122/128. When purified to at least substantiallyremove surfactant or another emulsion stabilizer, the emulsionstabilizers 106 may be present in the particles 128 at less than 0.01 wt% (or 0 wt % to about 0.01 wt %, or 0 wt % to 0.001 wt %).

Upon forming thermoplastic particulates according to the disclosureherein, at least a portion of the nanoparticles, such as silicananoparticles, may be disposed as a coating upon the outer surface ofthe thermoplastic particulates. At least a portion of the surfactant, ifused, may be associated with the outer surface as well. The coating maybe disposed substantially uniformly upon the outer surface. As usedherein with respect to a coating, the term “substantially uniform”refers to even coating thickness in surface locations covered by thecoating composition (e.g., nanoparticles and/or surfactant),particularly the entirety of the outer surface. The emulsion stabilizers106 may form a coating that covers at least 5% (or about 5% to about100%, or about 5% to about 25%, or about 20% to about 50%, or about 40%to about 70%, or about 50% to about 80%, or about 60% to about 90%, orabout 70% to about 100%) of the surface area of the particles 122/128.When purified to at least substantially remove surfactant or anotheremulsion stabilizer, the emulsion stabilizers 106 may be present in theparticles 128 at less than 25% (or 0% to about 25%, or about 0.1% toabout 5%, or about 0.1% to about 1%, or about 1% to about 5%, or about1% to about 10%, or about 5% to about 15%, or about 10% to about 25%) ofthe surface area of the particles 128. The coverage of the emulsionstabilizers 106 on an outer surface of the particles 122/128 may bedetermined using image analysis of the scanning electron microscopeimages (SEM micrographs). The emulsion stabilizers 106 may form acoating that covers at least 5% (or about 5% to about 100%, or about 5%to about 25%, or about 20% to about 50%, or about 40% to about 70%, orabout 50% to about 80%, or about 60% to about 90%, or about 70% to about100%) of the surface area of the particles 122/128. When purified to atleast substantially remove surfactant or another emulsion stabilizer,the emulsion stabilizers 106 may be present in the particles 128 at lessthan 25% (or 0% to about 25%, or about 0.1% to about 5%, or about 0.1%to about 1%, or about 1% to about 5%, or about 1% to about 10%, or about5% to about 15%, or about 10% to about 25%) of the surface area of theparticles 128. The coverage of the emulsion stabilizers 106 on an outersurface of the particles 122/128 may be determined using image analysisof the SEM micrographs.

The particles 122/128 may have a D10 of about 0.1 μm to about 125 μm (orabout 0.1 μm to about 5 μm, about 1 μm to about 10 μm, about 5 μm toabout 30 μm, or about 1 μm to about 25 μm, or about 25 μm to about 75μm, or about 50 μm to about 85 μm, or about 75 μm to about 125 μm), aD50 of about 0.5 μm to about 200 μm (or about 0.5 μm to about 10 μm, orabout 5 μm to about 50 μm, or about 30 μm to about 100 μm, or about 30μm to about 70 μm, or about 25 μm to about 50 μm, or about 50 μm toabout 100 μm, or about 75 μm to about 150 μm, or about 100 μm to about200 μm), and a D90 of about 3 μm to about 300 μm (or about 3 μm to about15 μm, or about 10 μm to about 50 μm, or about 25 μm to about 75 μm, orabout 70 μm to about 200 μm, or about 60 μm to about 150 μm, or about150 μm to about 300 μm), wherein D10<D50<D90. The particles 122/128 mayalso have a diameter span of about 0.2 to about 10 (or about 0.2 toabout 0.5, or about 0.4 to about 0.8, or about 0.5 to about 1.0, orabout 1 to about 3, or about 2 to about 5, or about 5 to about 10).Without limitation, diameter span values of 1.0 or greater areconsidered broad, and diameter spans values of 0.75 or less areconsidered narrow. Without limitation, diameter span values of 1.0 orgreater are considered broad, and diameter spans values of 0.75 or lessare considered narrow.

In a first nonlimiting example, the particles 122/128 may have a D10 ofabout 0.1 μm to about 10 μm, a D50 of about 0.5 μm to about 25 μm, and aD90 of about 3 μm to about 50 μm, wherein D10<D50<D90. Said particles122/128 may have a diameter span of about 0.2 to about 2.

In a second nonlimiting example, the particles 122/128 may have a D10 ofabout 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and aD90 of about 70 μm to about 120 μm, wherein D10<D50<D90. Said particles122/128 may have a diameter span of about 1.0 to about 2.5.

In a third nonlimiting example, the particles 122/128 may have a D10 ofabout 25 μm to about 60 μm, a D50 of about 60 μm to about 110 μm, and aD90 of about 110 μm to about 175 μm, wherein D10<D50<D90. Said particles122/128 may have a diameter span of about 0.6 to about 1.5.

In a fourth nonlimiting example, the particles 122/128 may have a D10 ofabout 75 μm to about 125 μm, a D50 of about 100 μm to about 200 μm, anda D90 of about 125 μm to about 300 μm, wherein D10<D50<D90. Saidparticles 122/128 may have a diameter span of about 0.2 to about 1.2.

In a fifth nonlimiting example, the particles 122/128 may have a D10 ofabout 1 μm to about 50 μm (or about 5 μm to about 30 μm, or about 1 μmto about 25 μm, or about 25 μm to about 50 μm), a D50 of about 25 μm toabout 100 μm (or about 30 μm to about 100 μm, or about 30 μm to about 70μm, or about 25 μm to about 50 μm, or about 50 μm to about 100 μm), anda D90 of about 60 μm to about 300 μm (or about 70 μm to about 200 μm, orabout 60 μm to about 150 μm, or about 150 μm to about 300 μm), whereinD10<D50<D90. The particles 122/128 may also have a diameter span ofabout 0.4 to about 3 (or about 0.6 to about 2, or about 0.4 to about1.5, or about 1 to about 3).

The particles 122/128 may have a circularity of about 0.9 or greater (orabout 0.90 to about 1.0, or about 0.93 to about 0.99, or about 0.95 toabout 0.99, or about 0.97 to about 0.99, or about 0.98 to 1.0).

The particles 122/128 may have an angle of repose of about 25° to about45° (or about 25° to about 35°, or about 30° to about 40°, or about 35°to about 45°).

The particles 122/128 may have a Hausner ratio of about 1.0 to about 1.5(or about 1.0 to about 1.2, or about 1.1 to about 1.3, or about 1.2 toabout 1.35, or about 1.3 to about 1.5).

The particles 122/128 may have a bulk density of about 0.3 g/cm³ toabout 0.8 g/cm³ (or about 0.3 g/cm³ to about 0.6 g/cm³, or about 0.4g/cm³ to about 0.7 g/cm³, or about 0.5 g/cm³ to about 0.6 g/cm³, orabout 0.5 g/cm³ to about 0.8 g/cm³).

Depending on the temperature and shear rate of processing 112 and thecomposition and relative concentrations of the components 102, 104, and106, different shapes of the structures that compose the particles122/128 have been observed. Typically, the particles 122/128 comprisesubstantially spherical particles (having a circularity of about 0.97 orgreater). However, other structures including disc and elongatedstructures have been observed in the particles 122/128. Therefore, theparticles 122/128 may comprise one or more of: (a) substantiallyspherical particles having a circularity of 0.97 or greater, (b) discstructures having an aspect ratio of about 2 to about 10, and (c)elongated structures having an aspect ratio of 10 or greater. Each ofthe (a), (b), and (c) structures have emulsion stabilizers dispersed onan outer surface of the (a), (b), and (c) structures and/or embedded inan outer portion of the (a), (b), and (c) structures. At least some ofthe (a), (b), and (c) structures may be agglomerated. For example, the(c) elongated structures may be laying on the surface of the (a)substantially spherical particles.

The particles 122/128 may have a sintering window that is within 10° C.,preferably within 5° C., of the sintering window of the thermoplasticpolymer 102 (comprising one or more PP-polyamides and optionally one ormore other thermoplastic polymers).

3-Dimensional Printing

The particles comprising PP-polyamides described herein may be useful ina variety of applications including 3-D printing. 3-D printing processesof the present disclosure may comprise: depositing PP-polyamideparticles of the present disclosure (e.g., particles comprising one ormore PP-polyamides and optionally one or more other thermoplasticpolymers) upon a surface in a specified shape, and once deposited,heating at least a portion of the particles to promote consolidationthereof and form a consolidated body (object), such that theconsolidated body has a void percentage of about 1% or less after beingconsolidated. For example, heating and consolidation of thethermoplastic polymer particles may take place in a 3-D printingapparatus employing a laser, such that heating and consolidation takeplace by selective laser sintering.

Examples of objects that may be 3-D printed using the thermoplasticpolymer particles of the present disclosure include, but are not limitedto, containers (e.g., for food, beverages, cosmetics, personal carecompositions, medicine, and the like), shoe soles, toys, furniture partsand decorative home goods, plastic gears, screws, nuts, bolts, cableties, automotive parts, medical items, prosthetics, orthopedic implants,aerospace/aircraft-related parts, production of artifacts that aidlearning in education, 3-D anatomy models to aid in surgeries, robotics,biomedical devices (orthotics), home appliances, dentistry, electronics,sporting goods, and the like.

Other applications for particles comprising one or more PP-polyamides ofthe present disclosure may include, but are not limited to, use as afiller in paints and powder coatings, inkjet materials andelectrophotographic toners, and the like.

Example Embodiments

A first nonlimiting example embodiment is a method comprising:functionalizing metal oxide particles that are bound to a pigmentparticle with a compound having an epoxy (terminal, pendent, or includeboth terminal and pendent of such group) to produce a surface treatedpigment having a pendent epoxy; and reacting the pendent epoxy with apolyamide to yield a pigment-pendent polyamide (PP-polyamide). The firstnonlimiting example embodiment may further include one or more of:Element 1: wherein the compound having the epoxide is selected from thegroup consisting of: (3-glycidoxypropyl)trimethoxysilane,(3-glycidoxypropyl)triethoxysilane,diethoxy(3-glycidyloxypropyl)methylsilane and1,3-bis(3-dlycidyloxypropyl)tetramethylsiloxane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane,3-glycidoxypropyl methyldiethoxysilane, 5,6-epoxyhexyltriethoxysilane,and any combination thereof; Element 2: wherein the metal oxideparticles comprise one or more selected from the group consisting of:titanium dioxide, a titanium suboxide, a titanium oxynitride, Al₂O₃,Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO, zirconium oxide, and an irontitanium oxide; Element 3: wherein the pigment particle comprises one ormore selected from the group consisting of: synthetic mica, naturalmica, talc, sericite, kaolin, glass, SiO₂ flakes, Al₂O₃ flakes, glassflakes, acicular pigments, CaSO₄, iron oxides, chromium oxides, carbonblack, metal effect pigments, optically variable pigments, liquidcrystal polymer pigments, and holographic pigments; Element 4: whereinthe polyamide is selected from the group consisting of: polycaproamide,poly(hexamethylene succinamide), polyhexamethylene adipamide,polypentamethylene adipamide, polyhexamethylene sebacamide,polyundecaamide, polydodecaamide, polyhexamethylene terephthalamide,nylon 10,10, nylon 10,12, nylon 10,14, nylon 10,18, nylon 6,18, nylon6,12, nylon 6,14, nylon 12,12, a semi-aromatic polyamide, an aromaticpolyamide, any copolymer thereof, and any combination thereof; Element5: wherein the reacting of the pendent epoxy with a polyamide is atabout 70° C. to about 200° C.; and Element 6: wherein a weight ratio ofthe pigment to the polyamide is about 1:10 to about 1:1000. Examples ofcombinations include, but are not limited to, Element 1 in combinationwith one or more of Elements 2-6; Element 2 in combination with one ormore of Elements 3-6; Element 3 in combination with one or more ofElements 4-6; and two or more of Elements 4-6 in combination.

A second nonlimiting example embodiment is the PP-polyamide producedaccording to the method of the first nonlimiting example embodiment(optionally including one or more of Elements 1-6).

A third nonlimiting example embodiment is a method comprising:functionalizing metal oxide particles that are bound to a pigmentparticle with a silica particle having a carboxylic acid (terminal,pendent, or include both terminal and pendent of such group) surfacetreatment to produce a surface treated pigment having a pendentcarboxylic acid; converting the pendent carboxylic acid to a pendentacid chloride; and reacting the pendent acid chloride with a polyamideto yield a pigment-pendent polyamide (PP-polyamide). The thirdnonlimiting example embodiment can further include one or more of:Element 7: wherein the metal oxide particles comprise one or moreselected from the group consisting of: titanium dioxide, a titaniumsuboxide, a titanium oxynitride, Al₂O₃, Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, ZnO,CuO, NiO, zirconium oxide, and an iron titanium oxide; Element 8:wherein the pigment particle comprises one or more selected from thegroup consisting of: synthetic mica, natural mica, talc, sericite,kaolin, glass, SiO₂ flakes, Al₂O₃ flakes, glass flakes, acicularpigments, CaSO₄, iron oxides, chromium oxides, carbon black, metaleffect pigments, optically variable pigments, liquid crystal polymerpigments, and holographic pigments; Element 9: wherein the silicaparticle having the carboxylic acid surface treatment comprises one ormore selected from the group consisting of:3-aminopropyl-(3-oxobutanoic) acid functionalized silica,3-propylsulphonic acid-functionalized silica gel, propylcarboxylic acidfunctionalized silica, triaminetetraacetic acid-functionalized silicagel, propionyl chloride-functionalized silica gel, 3-carboxypropylfunctionalized silica gel, aminomethylphosphonic acid(AMPA)-functionalized silica gel, and1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid(DOTA)-functionalized silica gel; Element 10: wherein the polyamide isselected from the group consisting of: polycaproamide,poly(hexamethylene succinamide), polyhexamethylene adipamide,polypentamethylene adipamide, polyhexamethylene sebacamide,polyundecaamide, polydodecaamide, polyhexamethylene terephthalamide,nylon 10,10, nylon 10,12, nylon 10,14, nylon 10,18, nylon 6,18, nylon6,12, nylon 6,14, nylon 12,12, a semi-aromatic polyamide, an aromaticpolyamide, any copolymer thereof, and any combination thereof; Element11: wherein the reacting of the pendent acid chloride with the polyamidecomprises melt mixing the pigment particle having a functionality withthe pendent acid chloride with the polyamide for 15 minutes to about 1hour at about 125° C. to about 250° C.; and Element 12: wherein a weightratio of the pigment to the polyamide is about 1:10 to about 1:1000.Examples of combinations include, but are not limited to, Element 7 incombination with one or more of Elements 8-12; Element 8 in combinationwith one or more of Elements 9-12; Element 9 in combination with one ormore of Elements 10-12; and two or more of Elements 10-12 incombination.

A fourth nonlimiting example embodiment is the PP-polyamide producedaccording to the method of the third nonlimiting example embodiment(optionally including one or more of Elements 7-12).

A fifth nonlimiting example embodiment is a composition comprising: apolyamide having a pigment pendent from a backbone of the polyamide,wherein the pigment comprises metal oxide particles on the surface of apigment particle. The third nonlimiting example embodiment may furtherinclude one or more of: Element 13: wherein the polyamide is selectedfrom the group consisting of: polycaproamide, poly(hexamethylenesuccinamide), polyhexamethylene adipamide, polypentamethylene adipamide,polyhexamethylene sebacamide, polyundecaamide, polydodecaamide,polyhexamethylene terephthalamide, nylon 10,10, nylon 10,12, nylon10,14, nylon 10,18, nylon 6,18, nylon 6,12, nylon 6,14, nylon 12,12, asemi-aromatic polyamide, an aromatic polyamide, any copolymer thereof,and any combination thereof; Element 14: wherein a weight ratio of thepigment to the polyamide is about 1:10 to about 1:1000; and Element 15:wherein the pigment particle comprises one or more selected from thegroup consisting of: synthetic mica, natural mica, talc, sericite,kaolin, glass, SiO₂ flakes, Al₂O₃ flakes, glass flakes, acicularpigments, CaSO₄, iron oxides, chromium oxides, carbon black, metaleffect pigments, optically variable pigments, liquid crystal polymerpigments, and holographic pigments.

A sixth nonlimiting example embodiment is an object comprising thecomposition of the fifth nonlimiting example embodiment (optionallyincluding one or more of Elements 13-15), which may be produced by thefirst or third nonlimiting example embodiments.

A seventh nonlimiting example embodiment is a method comprising:depositing particles upon a surface in a specified shape, and oncedeposited, wherein the particles comprise the composition of the fifthnonlimiting example embodiment (optionally including one or more ofElements 13-15); and heating at least a portion of the particles topromote consolidation thereof and form a consolidated body. Further, theparticles of the seventh nonlimiting example embodiment may furthercomprise a thermoplastic polymer selected from the group consisting of:polyurethane, polyethylene, polypropylene, polyacetal, polycarbonate,polybutylene terephthalate, polyethylene terephthalate, polyethylenenaphthalate, polytrimethylene terephthalate, polyhexamethyleneterephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethene,polyester, polyether, polyether sulfone, polyetherether ketone,polyacrylate, polymethacrylate, polyimide, acrylonitrile butadienestyrene, polyphenylene sulfide, vinyl polymer, polyarylene ether,polyarylene sulfide, polysulfone, polyether ketone, polyamide-imide,polyetherimide, polyetherester, copolymers comprising a polyether blockand a polyamide block, grafted or ungrafted thermoplastic polyolefin,functionalized or nonfunctionalized ethylene/vinyl monomer polymer,functionalized or nonfunctionalized ethylene/alkyl (meth)acrylate,functionalized or nonfunctionalized (meth)acrylic acid polymer,functionalized or nonfunctionalized ethylene/vinyl monomer/alkyl(meth)acrylate terpolymer, ethylene/vinyl monomer/carbonyl terpolymer,ethylene/alkyl (meth)acrylate/carbonyl terpolymer,methylmethacrylate-butadiene-styrene type core-shell polymer,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) blockterpolymer, chlorinated or chlorosulphonated polyethylene,polyvinylidene fluoride, phenolic resin, poly(ethylene/vinyl acetate),polybutadiene, polyisoprene, styrenic block copolymer,polyacrylonitrile, silicone, and any combination thereof.

A eighth nonlimiting example embodiment is a method comprising: mixing amixture comprising a polyamide having a pigment pendent from a backboneof the polyamide (PP-polyamide), a carrier fluid that is immiscible withthe PP-polyamide, and optionally an emulsion stabilizer at a temperaturegreater than a melting point or softening temperature of thePP-polyamide and at a shear rate sufficiently high to disperse thePP-polyamide in the carrier fluid; and cooling the mixture to below themelting point or softening temperature of the PP-polyamide to formsolidified particles comprising the PP-polyamide and, when present, theemulsion stabilizer associated with an outer surface of the solidifiedparticles.

A ninth nonlimiting example embodiment is a composition comprising:solidified particles comprising a polyamide having a pigment pendentfrom a backbone of the polyamide (PP-polyamide) and having a circularityof about 0.90 to about 1.0.

The eighth and ninth example embodiments may include one or more of:Element 16: wherein the emulsion stabilizer is included in the mixture(or wherein the solidified particles further comprise an emulsionstabilizer), and wherein the emulsion stabilizer associated with anouter surface of the solidified particles; Element 17: Element 16 andwherein at least some of the solidified particles have a void comprisingthe emulsion stabilizer at a void/polymer interface; Element 18: Element17 and wherein the void contains the carrier fluid; Element 19: Element17 and wherein the emulsion stabilizer comprises nanoparticles and thenanoparticles are embedded in the void/polymer interface; Element 20:Element 16 and wherein the solidified particles further compriseselongated structures on the surface of the solidified particles, whereinthe elongated structures comprises the PP-polyamide with the emulsionstabilizer associated with an outer surface of the elongated structures;Element 21: Element 16 and wherein the emulsion stabilizer forms acoating that covers less than 5% of the surface of the solidifiedparticles; Element 22: Element 16 and wherein the emulsion stabilizerforms a coating that covers at least 5% of the surface of the solidifiedparticles; Element 23: Element 16 and wherein the emulsion stabilizerforms a coating that covers at least 25% of the surface of thesolidified particles; Element 24: Element 16 and wherein the emulsionstabilizer forms a coating that covers at least 50% of the surface ofthe solidified particles; Element 25: Element 16 and wherein theemulsion stabilizer is present in the mixture (or the solidifiedparticles) at 0.05 wt % to 5 wt % by weight of the PP-polyamide; Element26: Element 16 and wherein the emulsion stabilizer comprisesnanoparticles and the nanoparticles have an average diameter of 1 nm to500 nm; Element 27: Element 16 and wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles comprise oxidenanoparticles; Element 28: Element 16 and wherein the emulsionstabilizer comprises nanoparticles and the nanoparticles comprise carbonblack; Element 29: Element 16 and wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles comprise polymernanoparticles; Element 30: wherein the mixture further comprises athermoplastic polymer that is not the PP-polyamide (or wherein thesolidified particles further comprise a thermoplastic polymer that isnot the PP-polyamide); Element 31: wherein the mixture further comprisesthe polyamide of the PP-polyamide but without a pigment pendenttherefrom (or wherein the solidified particles further comprise thepolyamide of the PP-polyamide but without a pigment pendent therefrom);Element 32: wherein the pigment is selected from the group consistingof: synthetic mica, natural mica, talc, sericite, kaolin, glass, SiO₂flakes, Al₂O₃ flakes, glass flakes, acicular pigments, CaSO₄, ironoxides, chromium oxides, carbon black, metal effect pigments, opticallyvariable pigments, liquid crystal polymer pigments, holographicpigments, and any combination thereof; Element 33: wherein the polyamideis selected from the group consisting of: polycaproamide,poly(hexamethylene succinamide), polyhexamethylene adipamide,polypentamethylene adipamide, polyhexamethylene sebacamide,polyundecaamide, polydodecaamide, polyhexamethylene terephthalamide,nylon 10,10, nylon 10,12, nylon 10,14, nylon 10,18, nylon 6,18, nylon6,12, nylon 6,14, nylon 12,12, a semi-aromatic polyamide, an aromaticpolyamide, any copolymer thereof, and any combination thereof; Element34: wherein a weight ratio of the pigment to the polyamide is about 1:10to about 1:1000; Element 35: wherein the solidified particles have a D10of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm,and a D90 of about 3 μm to about 300 μm, wherein D10<D50<D90; Element36: wherein the solidified particles have a diameter span of about 0.2to about 10; Element 37: wherein the solidified particles have a D10 ofabout 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and aD90 of about 70 μm to about 120 μm, wherein D10<D50<D90; Element 38:Element 37 and wherein the solidified particles have a diameter span ofabout 1.0 to about 2.5; Element 39: wherein the solidified particleshave a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about110 μm, and a D90 of about 110 μm to about 175 μm, wherein D10<D50<D90;Element 40: Element 39 and wherein the solidified particles have adiameter span of about 0.6 to about 1.5; Element 41: wherein thesolidified particles have a D10 of about 75 μm to about 125 μm, a D50 ofabout 100 μm to about 200 μm, and a D90 of about 125 μm to about 300 μm,wherein D10<D50<D90; Element 42: Element 41 and wherein the solidifiedparticles have a diameter span of about 0.2 to about 1.2; Element 43:wherein the solidified particles have a circularity of about 0.90 toabout 1.0; and Element 44: wherein the solidified particles have aHausner ratio of about 1.0 to about 1.5. Examples of combinationsinclude, but are not limited to, Element 16 in combination with one ormore of Elements 17-19; Element 16 in combination with one of Elements20-24 optionally in further combination with one or more of Elements17-19; Element 16 (optionally in combination with one of Elements 20-24and/or optionally in combination with one or more of Elements 17-19) incombination with one or more of Elements 25-29; Element 16 (optionallyin combination with one or more of Elements 17-29) in combination withone or more of Elements 30-44; two or more of Elements 30-34 incombination; one or more of Elements 30-34 in combination with one ormore of Elements 35-44; and Element 43 and/or 44 in combination with oneor more of Elements 35-42.

Further, the eighth nonlimiting example embodiment may further includeone or more of: Element 45: wherein the PP-polyamide is present in themixture at 5 wt % to 60 wt % of the mixture; Element 46: wherein thecarrier fluid is selected from the group consisting of: silicone oil,fluorinated silicone oils, perfluorinated silicone oils, polyethyleneglycols, paraffins, liquid petroleum jelly, vison oils, turtle oils,soya bean oils, perhydrosqualene, sweet almond oils, calophyllum oils,palm oils, parleam oils, grapeseed oils, sesame oils, maize oils,rapeseed oils, sunflower oils, cottonseed oils, apricot oils, castoroils, avocado oils, jojoba oils, olive oils, cereal germ oils, esters oflanolic acid, esters of oleic acid, esters of lauric acid, esters ofstearic acid, fatty esters, higher fatty acids, fatty alcohols,polysiloxanes modified with fatty acids, polysiloxanes modified withfatty alcohols, polysiloxanes modified with polyoxy alkylenes, and anycombination thereof; Element 47: wherein the silicone oil is selectedfrom the group consisting of: polydimethylsiloxane,methylphenylpolysiloxane, an alkyl modified polydimethylsiloxane, analkyl modified methylphenylpolysiloxane, an amino modifiedpolydimethylsiloxane, an amino modified methylphenylpolysiloxane, afluorine modified polydimethylsiloxane, a fluorine modifiedmethylphenylpolysiloxane, a polyether modified polydimethylsiloxane, apolyether modified methylphenylpolysiloxane, and any combinationthereof; Element 48: wherein the carrier fluid has a viscosity at 25° C.of 1000 cSt to 150,000 cSt; and Element 49: wherein the carrier fluidhas a density of 0.6 g/cm³ to 1.5 g/cm³. Examples of combinationsinclude, but are not limited to, one or more of Elements 16-44 incombination with one or more of Elements 45-49; and two or more ofElements 45-49.

Clauses

Clause 1. A method comprising: functionalizing metal oxide particlesthat are bound to a pigment particle with a compound having an epoxy(terminal, pendent, or include both terminal and pendent of such group)to produce a surface treated pigment having a pendent epoxy; andreacting the pendent epoxy with a polyamide to yield a pigment-pendentpolyamide (PP-polyamide).

Clause 2. The method of Clause 1, wherein the compound having theepoxide is selected from the group consisting of:(3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane,diethoxy(3-glycidyloxypropyl)methylsilane and1,3-bis(3-dlycidyloxypropyl)tetramethylsiloxane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane,3-glycidoxypropyl methyldiethoxysilane, 5,6-epoxyhexyltriethoxysilane,and any combination thereof.

Clause 3. The method of Clause 1, wherein the metal oxide particlescomprise one or more selected from the group consisting of: titaniumdioxide, a titanium suboxide, a titanium oxynitride, Al₂O₃, Fe₂O₃,Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO, zirconium oxide, and an iron titaniumoxide.

Clause 4. The method of Clause 1, wherein the pigment particle comprisesone or more selected from the group consisting of: synthetic mica,natural mica, talc, sericite, kaolin, glass, SiO₂ flakes, Al₂O₃ flakes,glass flakes, acicular pigments, CaSO₄, iron oxides, chromium oxides,carbon black, metal effect pigments, optically variable pigments, liquidcrystal polymer pigments, and holographic pigments.

Clause 5. The method of Clause 1, wherein the polyamide is selected fromthe group consisting of: polycaproamide, poly(hexamethylenesuccinamide), polyhexamethylene adipamide, polypentamethylene adipamide,polyhexamethylene sebacamide, polyundecaamide, polydodecaamide,polyhexamethylene terephthalamide, nylon 10,10, nylon 10,12, nylon10,14, nylon 10,18, nylon 6,18, nylon 6,12, nylon 6,14, nylon 12,12, asemi-aromatic polyamide, an aromatic polyamide, any copolymer thereof,and any combination thereof.

Clause 6. The method of Clause 1, wherein the reacting of the pendentepoxy with a polyamide is at about 70° C. to about 200° C.

Clause 7. The method of Clause 1, wherein a weight ratio of the pigmentto the polyamide is about 1:10 to about 1:1000.

Clause 8. A method comprising: functionalizing metal oxide particlesthat are bound to a pigment particle with a silica particle having acarboxylic acid (terminal, pendent, or include both terminal and pendentof such group) surface treatment to produce a surface treated pigmenthaving a pendent carboxylic acid; converting the pendent carboxylic acidto a pendent acid chloride; and reacting the pendent acid chloride witha polyamide to yield a pigment-pendent polyamide (PP-polyamide).

Clause 9. The method of Clause 8, wherein the metal oxide particlescomprise one or more selected from the group consisting of: titaniumdioxide, a titanium suboxide, a titanium oxynitride, Al₂O₃, Fe₂O₃,Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO, zirconium oxide, and an iron titaniumoxide.

Clause 10. The method of Clause 8, wherein the pigment particlecomprises one or more selected from the group consisting of: syntheticmica, natural mica, talc, sericite, kaolin, glass, SiO₂ flakes, Al₂O₃flakes, glass flakes, acicular pigments, CaSO₄, iron oxides, chromiumoxides, carbon black, metal effect pigments, optically variablepigments, liquid crystal polymer pigments, and holographic pigments.

Clause 11. The method of Clause 8, wherein the silica particle havingthe carboxylic acid surface treatment comprises one or more selectedfrom the group consisting of: 3-aminopropyl-(3-oxobutanoic) acidfunctionalized silica, 3-propylsulphonic acid-functionalized silica gel,propylcarboxylic acid functionalized silica, triaminetetraaceticacid-functionalized silica gel, propionyl chloride-functionalized silicagel, 3-carboxypropyl functionalized silica gel, aminomethylphosphonicacid (AMPA)-functionalized silica gel, and1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid(DOTA)-functionalized silica gel.

Clause 12. The method of Clause 8, wherein the polyamide is selectedfrom the group consisting of: polycaproamide, poly(hexamethylenesuccinamide), polyhexamethylene adipamide, polypentamethylene adipamide,polyhexamethylene sebacamide, polyundecaamide, polydodecaamide,polyhexamethylene terephthalamide, nylon 10,10, nylon 10,12, nylon10,14, nylon 10,18, nylon 6,18, nylon 6,12, nylon 6,14, nylon 12,12, asemi-aromatic polyamide, an aromatic polyamide, any copolymer thereof,and any combination thereof.

Clause 13. The method of Clause 8, wherein the reacting of the pendentacid chloride with the polyamide comprises melt mixing the pigmentparticle having a functionality with the pendent acid chloride with thepolyamide for 15 minutes to about 1 hour at about 125° C. to about 250°C.

Clause 14. The method of Clause 8, wherein a weight ratio of the pigmentto the polyamide is about 1:10 to about 1:1000.

Clause 15. A composition comprising: a polyamide having a pigmentpendent from a backbone of the polyamide, wherein the pigment comprisesmetal oxide particles on the surface of a pigment particle.

Clause 16. The composition of Clause 15, wherein the polyamide isselected from the group consisting of: polycaproamide,poly(hexamethylene succinamide), polyhexamethylene adipamide,polypentamethylene adipamide, polyhexamethylene sebacamide,polyundecaamide, polydodecaamide, polyhexamethylene terephthalamide,nylon 10,10, nylon 10,12, nylon 10,14, nylon 10,18, nylon 6,18, nylon6,12, nylon 6,14, nylon 12,12, a semi-aromatic polyamide, an aromaticpolyamide, any copolymer thereof, and any combination thereof.

Clause 17. The composition of Clause 15, wherein a weight ratio of thepigment to the polyamide is about 1:10 to about 1:1000.

Clause 18. The composition of Clause 15, wherein the pigment particlecomprises one or more selected from the group consisting of: syntheticmica, natural mica, talc, sericite, kaolin, glass, SiO₂ flakes, Al₂O₃flakes, glass flakes, acicular pigments, CaSO₄, iron oxides, chromiumoxides, carbon black, metal effect pigments, optically variablepigments, liquid crystal polymer pigments, and holographic pigments.

Clause 19. An article comprising: the composition of Clause 15.

Clause 20. A method comprising: depositing particles upon a surface in aspecified shape, and once deposited, wherein the particles comprise thepolyamide of one of claims 15-18; and heating at least a portion of theparticles to promote consolidation thereof and form a consolidated body.

Clause 21. The method of Clause 20, wherein the particles furthercomprise a thermoplastic polymer selected from the group consisting of:polyurethane, polyethylene, polypropylene, polyacetal, polycarbonate,polybutylene terephthalate, polyethylene terephthalate, polyethylenenaphthalate, polytrimethylene terephthalate, polyhexamethyleneterephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethene,polyester, polyether, polyether sulfone, polyetherether ketone,polyacrylate, polymethacrylate, polyimide, acrylonitrile butadienestyrene, polyphenylene sulfide, vinyl polymer, polyarylene ether,polyarylene sulfide, polysulfone, polyether ketone, polyamide-imide,polyetherimide, polyetherester, copolymers comprising a polyether blockand a polyamide block, grafted or ungrafted thermoplastic polyolefin,functionalized or nonfunctionalized ethylene/vinyl monomer polymer,functionalized or nonfunctionalized ethylene/alkyl (meth)acrylate,functionalized or nonfunctionalized (meth)acrylic acid polymer,functionalized or nonfunctionalized ethylene/vinyl monomer/alkyl(meth)acrylate terpolymer, ethylene/vinyl monomer/carbonyl terpolymer,ethylene/alkyl (meth)acrylate/carbonyl terpolymer,methylmethacrylate-butadiene-styrene type core-shell polymer,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) blockterpolymer, chlorinated or chlorosulphonated polyethylene,polyvinylidene fluoride, phenolic resin, poly(ethylene/vinyl acetate),polybutadiene, polyisoprene, styrenic block copolymer,polyacrylonitrile, silicone, and any combination thereof.

Clause 22. A method comprising: mixing a mixture comprising a polyamidehaving a pigment pendent from a backbone of the polyamide(PP-polyamide), a carrier fluid that is immiscible with thePP-polyamide, and optionally an emulsion stabilizer at a temperaturegreater than a melting point or softening temperature of thePP-polyamide and at a shear rate sufficiently high to disperse thePP-polyamide in the carrier fluid; and cooling the mixture to below themelting point or softening temperature of the PP-polyamide to formsolidified particles comprising the PP-polyamide and, when present, theemulsion stabilizer associated with an outer surface of the solidifiedparticles.

Clause 23. The method of Clause 22, wherein the emulsion stabilizer isincluded in the mixture, and wherein the emulsion stabilizer associatedwith an outer surface of the solidified particles.

Clause 24. The method of Clause 23, wherein emulsion stabilizercomprises nanoparticles, and wherein the nanoparticles are embedded inthe outer surface of the solidified particles.

Clause 25. The method of Clause 22, wherein the mixture furthercomprises a thermoplastic polymer that is not the PP-polyamide.

Clause 26. The method of Clause 22, wherein the mixture furthercomprises the polyamide of the PP-polyamide but without a pigmentpendent therefrom.

Clause 27. The method of Clause 22, wherein the pigment is selected fromthe group consisting of: synthetic mica, natural mica, talc, sericite,kaolin, glass, SiO₂ flakes, Al₂O₃ flakes, glass flakes, acicularpigments, CaSO₄, iron oxides, chromium oxides, carbon black, metaleffect pigments, optically variable pigments, liquid crystal polymerpigments, holographic pigments, and any combination thereof.

Clause 28. The method of Clause 22, wherein the polyamide is selectedfrom the group consisting of: polycaproamide, poly(hexamethylenesuccinamide), polyhexamethylene adipamide, polypentamethylene adipamide,polyhexamethylene sebacamide, polyundecaamide, polydodecaamide,polyhexamethylene terephthalamide, nylon 10,10, nylon 10,12, nylon10,14, nylon 10,18, nylon 6,18, nylon 6,12, nylon 6,14, nylon 12,12, asemi-aromatic polyamide, an aromatic polyamide, any copolymer thereof,and any combination thereof.

Clause 29. The method of Clause 22, wherein a weight ratio of thepigment to the polyamide is about 1:10 to about 1:1000.

Clause 30. The method of Clause 22, wherein at least some of thesolidified particles have a void comprising the emulsion stabilizer at avoid/polymer interface.

Clause 31. The method of Clause 30, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles are embedded in thevoid/polymer interface.

Clause 32. The method of Clause 30, wherein the void contains thecarrier fluid.

Clause 33. The method of Clause 22, wherein the solidified particlesfurther comprises elongated structures on the surface of the solidifiedparticles, wherein the elongated structures comprises the PP-polyamidewith the emulsion stabilizer associated with an outer surface of theelongated structures.

Clause 34. The method of Clause 22, wherein the emulsion stabilizer isincluded and forms a coating that covers less than 5% of the surface ofthe solidified particles.

Clause 35. The method of Clause 22, wherein the emulsion stabilizer isincluded and forms a coating that covers at least 5% of the surface ofthe solidified particles.

Clause 36. The method of Clause 22, wherein the emulsion stabilizer isincluded and forms a coating that covers at least 25% of the surface ofthe solidified particles.

Clause 37. The method of Clause 22, wherein the emulsion stabilizer isincluded and forms a coating that covers at least 50% of the surface ofthe solidified particles.

Clause 38. The method of Clause 22, wherein the PP-polyamide is presentin the mixture at 5 wt % to 60 wt % of the mixture.

Clause 39. The method of Clause 22, wherein the emulsion stabilizer isincluded and is present in the mixture at 0.05 wt % to 5 wt % by weightof the PP-polyamide.

Clause 40. The method of Clause 22, wherein the emulsion stabilizer isincluded and comprises nanoparticles and the nanoparticles have anaverage diameter of 1 nm to 500 nm.

Clause 41. The method of Clause 22, wherein the carrier fluid isselected from the group consisting of: silicone oil, fluorinatedsilicone oils, perfluorinated silicone oils, polyethylene glycols,paraffins, liquid petroleum jelly, vison oils, turtle oils, soya beanoils, perhydrosqualene, sweet almond oils, calophyllum oils, palm oils,parleam oils, grapeseed oils, sesame oils, maize oils, rapeseed oils,sunflower oils, cottonseed oils, apricot oils, castor oils, avocadooils, jojoba oils, olive oils, cereal germ oils, esters of lanolic acid,esters of oleic acid, esters of lauric acid, esters of stearic acid,fatty esters, higher fatty acids, fatty alcohols, polysiloxanes modifiedwith fatty acids, polysiloxanes modified with fatty alcohols,polysiloxanes modified with polyoxy alkylenes, and any combinationthereof.

Clause 42. The method of Clause 41, wherein the silicone oil is selectedfrom the group consisting of: polydimethylsiloxane,methylphenylpolysiloxane, an alkyl modified polydimethylsiloxane, analkyl modified methylphenylpolysiloxane, an amino modifiedpolydimethylsiloxane, an amino modified methylphenylpolysiloxane, afluorine modified polydimethylsiloxane, a fluorine modifiedmethylphenylpolysiloxane, a polyether modified polydimethylsiloxane, apolyether modified methylphenylpolysiloxane, and any combinationthereof.

Clause 43. The method of Clause 22, wherein the carrier fluid has aviscosity at 25° C. of 1000 cSt to 150,000 cSt.

Clause 44. The method of Clause 22, wherein the carrier fluid has adensity of 0.6 g/cm³ to 1.5 g/cm³.

Clause 45. The method of Clause 22, wherein mixing occurs in anextruder.

Clause 46. The method of Clause 22, wherein mixing occurs in a stirredreactor.

Clause 47. The method of Clause 22, wherein the mixture furthercomprises a surfactant.

Clause 448. The method of Clause 22, wherein the solidified particleshave a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm toabout 200 μm, and a D90 of about 3 μm to about 300 μm, whereinD10<D50<D90.

Clause 49. The method of Clause 22, wherein the solidified particleshave a diameter span of about 0.2 to about 10.

Clause 50. The method of Clause 22, wherein the solidified particleshave a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm to about70 μm, and a D90 of about 70 μm to about 120 μm, wherein D10<D50<D90.

Clause 51. The method of Clause 50, wherein the solidified particleshave a diameter span of about 1.0 to about 2.5.

Clause 52. The method of Clause 22, wherein the solidified particleshave a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about110 μm, and a D90 of about 110 μm to about 175 μm, wherein D10<D50<D90.

Clause 53. The method of Clause 52, wherein the solidified particleshave a diameter span of about 0.6 to about 1.5.

Clause 54. The method of Clause 22, wherein the solidified particleshave a D10 of about 75 μm to about 125 μm, a D50 of about 100 μm toabout 200 μm, and a D90 of about 125 μm to about 300 μm, whereinD10<D50<D90.

Clause 55. The method of Clause 54, wherein the solidified particleshave a diameter span of about 0.2 to about 1.2.

Clause 56. The method of Clause 22, wherein the solidified particleshave a circularity of about 0.90 to about 1.0.

Clause 57. The method of Clause 22, wherein the solidified particleshave a Hausner ratio of about 1.0 to about 1.5.

Clause 58. The method of Clause 22, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles comprise oxidenanoparticles.

Clause 59. The method of Clause 22, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles comprise carbon black.

Clause 60. The method of Clause 22, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles comprise polymernanoparticles.

Clause 61. A composition comprising: particles comprising a polyamidehaving a pigment pendent from a backbone of the polyamide (PP-polyamide)and having a circularity of about 0.90 to about 1.0.

Clause 62. The composition of Clause 61, wherein the particles furthercomprise a thermoplastic polymer that is not the PP-polyamide.

Clause 63. The composition of Clause 61, wherein the particles furthercomprise the polyamide of the PP-polyamide but without a pigment pendenttherefrom.

Clause 64. The composition of Clause 61, wherein the particles furthercomprise an emulsion stabilizer associated with an outer surface of theparticles.

Clause 65. The composition of Clause 61, wherein at least some of theparticles have a void comprising the emulsion stabilizer at avoid/polymer interface.

Clause 66. The composition of Clause 65, wherein the emulsion stabilizercomprises nanoparticles and the nanoparticles are embedded in thevoid/polymer interface.

Clause 67. The composition of Clause 65, wherein the void contains thecarrier fluid.

Clause 68. The composition of Clause 61, wherein the particles furthercomprises elongated structures on the surface of the particles, whereinthe elongated structures comprises the PP-polyamide with the emulsionstabilizer associated with an outer surface of the elongated structures.

Clause 69. The composition of Clause 61, wherein the emulsion stabilizerforms a coating that covers less than 5% of the surface of thesolidified particles.

Clause 70. The composition of Clause 61, wherein the emulsion stabilizerforms a coating that covers at least 5% of the surface of the solidifiedparticles.

Clause 71. The composition of Clause 61, wherein the emulsion stabilizerforms a coating that covers at least 25% of the surface of thesolidified particles.

Clause 72. The composition of Clause 61, wherein the emulsion stabilizerforms a coating that covers at least 50% of the surface of thesolidified particles.

Clause 73. The composition of Clause 61, wherein the emulsion stabilizercomprises nanoparticles having an average diameter of 1 nm to 500 nm.

Clause 74. The composition of Clause 61, wherein the solidifiedparticles have a D10 of about 0.5 μm to about 125 μm, a D50 of about 1μm to about 200 μm, and a D90 of about 70 μm to about 300 μm, whereinD10<D50<D90.

Clause 75. The composition of Clause 61, wherein the solidifiedparticles have a diameter span of about 0.2 to about 10.

Clause 76. The composition of Clause 61, wherein the solidifiedparticles have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μmto about 70 μm, and a D90 of about 70 μm to about 120 μm, whereinD10<D50<D90.

Clause 77. The composition of Clause 76, wherein the solidifiedparticles have a diameter span of about 1.0 to about 2.5.

Clause 78. The composition of Clause 61, wherein the solidifiedparticles have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μmto about 110 μm, and a D90 of about 110 μm to about 175 μm, whereinD10<D50<D90.

Clause 79. The composition of Clause 78, wherein the solidifiedparticles have a diameter span of about 0.6 to about 1.5.

Clause 80. The composition of Clause 61, wherein the solidifiedparticles have a D10 of about 75 μm to about 125 μm, a D50 of about 100μm to about 200 μm, and a D90 of about 125 μm to about 300 μm, whereinD10<D50<D90.

Clause 81. The composition of Clause 80, wherein the solidifiedparticles have a diameter span of about 0.2 to about 1.2.

Clause 82. The composition of Clause 61, wherein the solidifiedparticles have a Hausner ratio of about 1.0 to about 1.5.

Clause 83. A method comprising: depositing the composition of Clause 61optionally in combination with other thermoplastic polymer particlesupon a surface in a specified shape; and once deposited, heating atleast a portion of the particles to promote consolidation thereof andform a consolidated body.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the present specification and associated claims areto be understood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the incarnations of the present inventions. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claim, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

One or more illustrative incarnations incorporating one or moreinvention elements are presented herein. Not all features of a physicalimplementation are described or shown in this application for the sakeof clarity. It is understood that in the development of a physicalembodiment incorporating one or more elements of the present invention,numerous implementation-specific decisions must be made to achieve thedeveloper's goals, such as compliance with system-related,business-related, government-related and other constraints, which varyby implementation and from time to time. While a developer's effortsmight be time-consuming, such efforts would be, nevertheless, a routineundertaking for those of ordinary skill in the art and having benefit ofthis disclosure.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsand steps.

To facilitate a better understanding of the embodiments of the presentinvention, the following examples of preferred or representativeembodiments are given. In no way should the following examples be readto limit, or to define, the scope of the invention.

EXAMPLES Prophetic Example 1: IRIODIN® 100 Silver Pearl Pigment Reactedwith (3-glycidyloxypropyl)trimethoxysilane and Crosslinked by PolyamideResin in Solution

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of IRIODIN® 100 Silver Pearlpigment (available from E. Merck KGaA, Darmstadt) suspended in 900 mL ofdeionized water and heated to 40° C. with vigorous stirring. Thesuspension is adjusted to pH of 3.3 using 2.5% hydrochloric acid and thetemperature is raised to 75° C.

Subsequently, 3.0 g of (3-glycidyloxypropyl)trimethoxysilane (availablefrom Millipore Sigma) is added over the course of 10 minutes and the pHis kept constant using the 2.5% hydrochloric acid solution. At the endof the addition, stirring is continued at 75° C. for 2 hours duringwhich the silane hydrolyzes and the resulting silanols associate withthe inorganic pigment surface.

Subsequently, the system is adjusted to a pH of 8.0 while maintainingthe reaction temperature of 75° C. using 2.5% sodium hydroxide solutionvery slowly over the course of 1 hour during which time the condensationreaction occurs and the resulting siloxane bonds to the pigment surfaceleaving the unreacted epoxy end group free for subsequentfunctionalization. Stirring is continued at 75° C. for an additional 1hour to complete the reaction and the pH falls to 7.0. The product isfiltered off using vacuum filtration, washed with deionized water anddried at 140° C. for approximately 16 hours.

Subsequently, 100 g of polyamide resin, such as nylon 6,6, is dissolvedin N-methyl-2-pyrrolidone (NMP) with vigorous agitation. To this mixtureis added 10 g of the epoxide functionalized IRIODIN® 100 Silver Pearlpigment from above and the reaction mixture with continuous agitation isincreased to 150° C. for 2 hours to facilitate the curing reaction ofthe amino functional groups of the polyamide resin with the pendentglycidyloxypropyl (epoxide) group coating the surface of IRIODIN® 100Silver Pearl pigment. After the polyamide resin has cured and coated thesuspended IRIODIN® 100 Silver Pearl pigment the solvent is removed byfiltering the particles using vacuum filtration and the material isthoroughly dried in a vacuum oven for 24 hours. Then a portion of thismixture is mixed with non-pigment-pendant polyamide in the Haakereaction with PDMS to form the particles.

Using 2.5 g of IRIODIN® 100 Silver Pearl pigment-pendent crosslinked bypolyamide resin onto the pigment surface and 27.5 g of nylon 6,6 is meltmixed with 150 g of polydimethylsiloxane (PDMS) of 60,000 specificviscosity by hot melt emulsification in a Haake mixer fitted with a 300ml mixing vessel. The mixer is heated to 230° C. and mixed at 200 rpmfor 20 minutes. Then, the mixture is discharged from the Haake onto acold surface to provide rapid quench cooling. The resultant mixture isthen filtered through a 90 mm WHATMAN® #1 paper filter (available fromSigmaAldrich) to separate the PP-polyamide particles from the carrierfluid. The PP-polyamide particles are washed three times with 1000 mL ofethyl acetate. The PP-polyamide particles are then allowed to air dryovernight in an aluminum pan in a fume hood. Optionally, the driedPP-polyamide particles can be screened through a 150-μm sieve. ThePP-polyamide particles are then characterized for size with a MalvernMASTERSIZER™ 3000 and morphology with SEM micrographs. The D50 (μm) ispredicted to be around 50 μm with a span of about 0.85.

Prophetic Example 2: BLONDIEE® Metallic Super Gold Pigment Reacted with(3-glycidyloxypropyl)trimethoxysilane and In-Situ Crosslinking withPolyamide Resin

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of BLONDIEE® Metallic SuperGold pigment, product code N-2002S (available from Creation of QualityValue Company Ltd.) suspended in 900 mL of deionized water and heated to40° C. with vigorous stirring. The suspension is adjusted to pH of 3.3using 2.5% hydrochloric acid and the temperature is raised to 75° C.

Subsequently, 3.0 g of (3-glycidyloxypropyl)trimethoxysilane (availablefrom Millipore Sigma) is added over the course of 10 minutes and the pHis kept constant using the 2.5% hydrochloric acid solution. At the endof the addition, stirring is continued at 75° C. for 2 hours duringwhich the silane hydrolyzes and the resulting silanols associate withthe inorganic pigment surface.

Subsequently, the system is adjusted to a pH of 8.0 while maintainingthe reaction temperature of 75° C. using 2.5% sodium hydroxide solutionvery slowly over the course of 1 hour during which time the condensationreaction occurs and the resulting siloxane bonds to the pigment surfaceleaving the unreacted epoxy end group free for subsequentfunctionalization. Stirring is continued at 75° C. for an additional 1hour to complete the reaction and the pH falls to 7.0. The product isfiltered off using vacuum filtration, washed with deionized water anddried at 140° C. for approximately 16 hours.

Subsequently, 50 g of polyamide resin such as nylon 6,6 is melt mixedwith 10 g of the above epoxide surface functionalized mica pigmentBlondiee® Metallic Super Gold melt mixed in the Haake mixer at 150° C.to 200° C. for 20 to 30 minutes to facilitate the crosslinking reactionof the epoxide with the amino group of the polyamide resin. Theresulting pigment-pendent polyamide resin concentrate is discharged fromthe Haake mixer, cooled and grounded into a fine powder for subsequentincorporation into pigmented polyamide micron particles.

Using 1.5 g of BLONDIEE® Metallic Super Gold pigment-pendent crosslinkedpolyamide resin onto the pigment surface and 28.5 g of nylon 6,6 is meltmixed with 150 g of polydimethylsiloxane (PDMS) of 30,000 specificviscosity by hot melt emulsification in a Haake mixer fitted with a 300ml mixing vessel. The mixer is heated to 230° C. and mixed at 200 rpmfor 20 minutes.

Then, the mixture is discharged from the Haake onto a cold surface toprovide rapid quench cooling. The resultant mixture is then filteredthrough a 90 mm WHATMAN® #1 paper filter (available from SigmaAldrich)to separate the PP-polyamides particles from the carrier fluid. Theparticles are washed three times with 1000 mL of ethyl acetate. Theparticles are then allowed to air dry overnight in an aluminum pan in afume hood. Optionally, the dried particles can be screened through a150-μm sieve. The PP-polyamide particles are then characterized for sizewith a Malvern MASTERSIZER™ 3000 and morphology with SEM micrographs.The D50 (μm) is predicted to be around 65 μm with a span of about 1.20.

Prophetic Example 3: REFLEX® 100 Sparkle Violet Pigment Reacted with(3-glycidyloxypropyl)trimethoxysilane and Crosslinked by Polyamide Resinin Solution

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of REFLEX® 100 SparkleViolet R-706E pigment (available from Creation of Quality Value CompanyLtd.) suspended in 900 mL of deionized water and heated to 40° C. withvigorous stirring. The suspension is adjusted to pH of 3.3 using 2.5%hydrochloric acid and the temperature is raised to 75° C.

Subsequently, 3.0 g of (3-glycidyloxypropyl)trimethoxysilane (availablefrom Millipore Sigma) is added over the course of 10 minutes and the pHis kept constant using the 2.5% hydrochloric acid solution. At the endof the addition, stirring is continued at 75° C. for 2 hours duringwhich the silane hydrolyzes and the resulting silanols associate withthe inorganic pigment surface.

Subsequently, the system is adjusted to a pH of 8.0 while maintainingthe reaction temperature of 75° C. using 2.5% sodium hydroxide solutionvery slowly over the course of 1 hour during which time the condensationreaction occurs and the resulting siloxane bonds to the pigment surfaceleaving the unreacted epoxy end group free for subsequentfunctionalization. Stirring is continued at 75° C. for an additional 1hour to complete the reaction and the pH falls to 7.0. The product isfiltered off using vacuum filtration, washed with deionized water anddried at 140° C. for approximately 16 hours.

Subsequently, 100 g of polyamide resin such as nylon 6,6 is dissolved inN-methyl-2-pyrrolidone (NMP) with vigorous agitation. To this mixture isadded 10 g of the epoxide functionalized REFLEX® 100 Sparkle VioletR-706E pigment from above and the reaction mixture with continuousagitation is increased to 150° C. for 2 hours to facilitate the curingreaction of the amino functional groups of the polyamide resin with thependent glycidyloxypropyl (epoxide) group coating the surface of REFLEX®100 Sparkle Violet R-706E pigment. After the polyamide resin has curedand coated the suspended REFLEX® 100 Sparkle Violet R-706E pigment thesolvent is removed by filtering the particles using vacuum filtrationand the material is thoroughly dried in a vacuum oven for 24 hours. Thena portion of this mixture is mixed with non-pigment-pendant polyamide inthe Haake reaction with PDMS to form the particles.

Using 50 g of REFLEX® 100 Sparkle Violet R-706E pigment-pendentcrosslinked by polyamide resin onto the pigment surface and 550 g ofnylon 6,6 is melt mixed with 2000 g of polydimethylsiloxane (PDMS) of10,000 specific viscosity by hot melt emulsification in a 25 mmtwin-screw extruder (Werner & Pfleiderer ZSK-25). The polymer pelletsare added to the extruder first, brought to the temperature of 230° C.and rpm of 900, and then preheated carrier fluid having AEROSIL® R812Ssilica nanoparticles (1.1-wt. % relative to PP-polyamide) dispersedtherein is added to the molten polymer in the extruder.

Then the mixture is discharged into a container and allowed to cool toroom temperature over several hours. The resultant mixture is thenfiltered through a 90 mm WHATMAN® #1 paper filter (available fromSigmaAldrich) to separate the PP-polyamides particles from the carrierfluid. The particles are washed three times with 2000 mL of ethylacetate. The particles are then allowed to dry overnight in vacuum ovenat ambient temperature. Optionally, the dried particles can be screenedthrough a 150-μm sieve. The PP-polyamide particles are thencharacterized for size with a Malvern MASTERSIZER™ 3000 and morphologywith SEM micrographs. The D50 (μm) is predicted to be around 75 μm witha span of about 1.30.

Prophetic Example 4: Reflex® Glitter Blue R-781E Pigment Reacted with(3-glycidyloxypropyl)trimethoxysilane and In-Situ Crosslinking withPolyamide Resin

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of Reflex® Glitter Bluepigment, product code R-781E (available from Creation of Quality ValueCompany Ltd.) suspended in 900 mL of deionized water and heated to 40°C. with vigorous stirring. The suspension is adjusted to pH of 3.3 using2.5% hydrochloric acid and the temperature is raised to 75° C.

Subsequently, 3.0 g of (3-glycidyloxypropyl)trimethoxysilane (availablefrom Millipore Sigma) is added over the course of 10 minutes and the pHis kept constant using the 2.5% hydrochloric acid solution. At the endof the addition, stirring is continued at 75° C. for 2 hours duringwhich the silane hydrolyzes and the resulting silanols associate withthe inorganic pigment surface.

Subsequently, the system is adjusted to a pH of 8.0 while maintainingthe reaction temperature of 75° C. using 2.5% sodium hydroxide solutionvery slowly over the course of 1 hour during which time the condensationreaction occurs and the resulting siloxane bonds to the pigment surfaceleaving the unreacted epoxy end group free for subsequentfunctionalization. Stirring is continued at 75° C. for an additional 1hour to complete the reaction and the pH falls to 7.0. The product isfiltered off using vacuum filtration, washed with deionized water anddried at 140° C. for approximately 16 hours.

Subsequently, 50 g of polyamide resin such as nylon 6,6 is melt mixedwith 10 g of the above epoxide surface functionalized mica pigmentReflex® Glitter Blue R-871E melt mixed in the Haake mixer at 150° C. to200° C. for 20 to 30 minutes to facilitate the crosslinking reaction ofthe epoxide with the amino group of the polyamide resin. The resultingpigment-pendent polyamide resin concentrate is discharged from the Haakemixer, cooled and grounded into a fine powder for subsequentincorporation into pigmented polyamide micron particles.

Using 30 g of REFLEX® Glitter Blue R-871E pigment-pendent crosslinkedpolyamide resin onto the pigment surface and 570 g of nylon 6,6 is meltmixed with 2000 g of polydimethylsiloxane (PDMS) of 10,000 specificviscosity by hot melt emulsification in a 25 mm twin-screw extruder(Werner & Pfleiderer ZSK-25). The polymer pellets are added to theextruder first, brought to the temperature of 230° C. and rpm of 900,and then preheated carrier fluid having AEROSIL® R812S silicananoparticles (1.1 wt % relative to PP-polyamide) dispersed therein isadded to the molten polymer in the extruder.

Then the mixture is discharged into a container and allowed to cool toroom temperature over several hours. The resultant mixture is thenfiltered through a 90 mm WHATMAN® #1 paper filter (available fromSigmaAldrich) to separate the PP-polyamides particles from the carrierfluid. The particles are washed three times with 2000 mL of ethylacetate. The particles are then allowed to dry overnight in vacuum ovenat ambient temperature. Optionally, the dried particles can be screenedthrough a 150-μm sieve. The PP-polyamide particles are thencharacterized for size with a Malvern MASTERSIZER™ 3000 and morphologywith SEM micrographs. The D50 (μm) is predicted to be around 65 μm witha span of about 1.10.

Prophetic Example 5: IRIODIN® 100 Silver Pearl Pigment Reacted with3-Aminopropyl(3-oxobutaonoic)acid Functionalized Silica Nanoparticlesand In-situ Crosslinked by Polyamide Resin

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of IRIODIN® 100 Silver Pearlpigment (available from E. Merck KGaA, Darmstadt, Germany) suspended in900 mL of deionized water and 100 mL of3-aminopropyl(3-oxobutaonoic)acid functionalized silica nanoparticles asa colloidal dispersion at 2.5 wt % loading in dimethylformamide (DMF)(available from Millipore Sigma). The mixture was heated to 40° C. withvigorous stirring for 4 hours to facilitate the adsorption of the silicananoparticles onto the surface of the pigment. The suspension is cooledto room temperature and filtered to remove the water and DMF solvent.The functionalized pigment particles with free carboxylic acidfunctional groups are dried in a vacuum oven at 40° C. for 24 hours toproduce a functionalized pigment powder.

A clear viscous stock solution (1.5 molar) of thionyl chloride (5.46 mL,0.075 mol) and benzotriazole (8.93 g, 0.075 mol) in 50 mL of drymethylene chloride was prepared at room temperature with mixing. Aportion of this solution (1.25 mmol) is added slowly to convert thependent carboxylic acid functional groups on the surface of the micapigment to acid chloride to enable curing with the amino polyamide groupin the polyamide resin.

The dried mica pigment IRIODIN® 100 Silver Pearl functionalized withsurface carboxylic acid (approximately 110 g) is suspended in 500 mL ofdry methylene chloride with constant agitation. To this mixture is added20 mL of the thionyl chloride-benzotriazole mixture slowly over 30minutes at room temperature. As the reaction proceeds benzotriazolehydrochloride salt starts to precipitate out of the solution indicatingthe conversion of the carboxylic acid is converted to the acid chloride.The reaction mixture is mixed for an additional 30 minutes and then themixture is filtered to remove the solvent and thoroughly washed withwater then dried in a vacuum oven for 24 hours.

Subsequently, 50 g of polyamide resin such as nylon 6,6 is melt mixedwith 10 g of the above acid chloride surface functionalized mica pigmentIRIODIN® 100 Silver Pearl melt mixed in the Haake mixer at 150° C. to200° C. for 20 to 30 minutes to facilitate the crosslinking reaction ofthe acid chloride with the amino group of the polyamide resin. Theresulting pigment-pendent polyamide resin concentrate is discharged fromthe Haake mixer, cooled and grounded into a fine powder for subsequentincorporation into pigmented polyamide micron particles.

Using 1.5 g of IRIODIN® 100 Silver Pearl pigment-pendent crosslinkedpolyamide resin onto the pigment surface and 28.5 g of nylon 6,6 is meltmixed with 150 g of polydimethylsiloxane (PDMS) of 30,000 specificviscosity containing AEROSIL® R812S silica nanoparticles (0.75 wt %relative to PP-polyamide) dispersed therein by hot melt emulsificationin a Haake mixer fitted with a 300 ml mixing vessel. The mixer is heatedto 230° C. and mixed at 200 rpm for 15 minutes.

Then, the mixture is discharged from the Haake onto a cold surface toprovide rapid quench cooling. The resultant mixture is then filteredthrough a 90 mm WHATMAN® #1 paper filter (available from SigmaAldrich)to separate the PP-polyamides particles from the carrier fluid. Theparticles are washed three times with 1000 mL of ethyl acetate. Theparticles are then allowed to air dry overnight in an aluminum pan in afume hood. Optionally, the dried particles can be screened through a150-μm sieve. The PP-polyamide particles are then characterized for sizewith a Malvern MASTERSIZER™ 3000 and morphology with SEM micrographs.The D50 (μm) is predicted to be around 55 μm with a span of about 1.10.

Prophetic Example 6: BLONDIEE® Metallic Super Gold Pigment Reacted with3-Aminopropyl(3-oxobutaonoic)acid Functionalized Silica Nanoparticlesand In-Situ Crosslinked by Polyamide Resin

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of BLONDIEE® Metallic SuperGold (available from Creation of Quality Value Company Ltd.) suspendedin 900 mL of deionized water and 100 mL of3-aminopropyl(3-oxobutaonoic)acid functionalized silica nanoparticles asa colloidal dispersion at 2.5 wt % loading in DMF (available fromMillipore Sigma). The mixture was heated to 40° C. with vigorousstirring for 4 hours to facilitate the adsorption of the silicananoparticles onto the surface of the pigment. The suspension is cooledto room temperature and filtered to remove the water and DMF solvent.The functionalized pigment particles with free carboxylic acidfunctional groups are dried in a vacuum oven at 40° C. for 24 hours toproduce a functionalized pigment powder.

A clear viscous stock solution (1.5 molar) of thionyl chloride (5.46 mL,0.075 mol) and benzotriazole (8.93 g, 0.075 mol) in 50 mL of drymethylene chloride was prepared at room temperature with mixing. Aportion of this solution (1.25 mmol) is added slowly to convert thependent carboxylic acid functional groups on the surface of the micapigment to acid chloride to enable curing with the amino polyamide groupin the polyamide resin.

The dried mica pigment BLONDIEE® Metallic Super Gold functionalized withsurface carboxylic acid (approximately 110 g) is suspended in 500 mL ofdry methylene chloride with constant agitation. To this mixture is added20 mL of the thionyl chloride-benzotriazole mixture slowly over 30minutes at room temperature. As the reaction proceeds benzotriazolehydrochloride salt starts to precipitate out of the solution indicatingthe conversion of the carboxylic acid is converted to the acid chloride.The reaction mixture is mixed for an additional 30 minutes and then themixture is filtered to remove the solvent and thoroughly washed withwater then dried in a vacuum oven for 24 hours.

Subsequently, 50 g of polyamide resin such as nylon 6,6 is melt mixedwith 10 g of the above acid chloride surface functionalized mica pigmentBlondiee® Metallic Super Gold melt mixed in the Haake mixer at 150° C.to 200° C. for 20 to 30 minutes to facilitate the crosslinking reactionof the acid chloride with the amino group of the polyamide resin. Theresulting pigment-pendent polyamide resin concentrate is discharged fromthe Haake mixer, cooled and grounded into a fine powder for subsequentincorporation into pigmented polyamide micron particles.

Using 1.5 g of BLONDIEE® Metallic Super Gold pigment-pendent crosslinkedpolyamide resin onto the pigment surface and 28.5 g of nylon 6,6 is meltmixed with 150 g of polydimethylsiloxane (PDMS) of 30,000 specificviscosity containing AEROSIL® R812S silica nanoparticles (1.00 wt %relative to PP-polyamide) dispersed therein by hot melt emulsificationin a Haake mixer fitted with a 300 ml mixing vessel. The mixer is heatedto 230° C. and mixed at 200 rpm for 15 minutes.

Then, the mixture is discharged from the Haake onto a cold surface toprovide rapid quench cooling. The resultant mixture is then filteredthrough a 90 mm WHATMAN® #1 paper filter (available from SigmaAldrich)to separate the PP-polyamides particles from the carrier fluid. Theparticles are washed three times with 1000 mL of ethyl acetate. Theparticles are then allowed to air dry overnight in an aluminum pan in afume hood. Optionally, the dried particles can be screened through a150-μm sieve. The PP-polyamide particles are then characterized for sizewith a Malvern MASTERSIZER™ 3000 and morphology with SEM micrographs.The D50 (μm) is predicted to be around 50 μm with a span of about 0.95.

Prophetic Example 7: REFLEX® 100 Sparkle Violet Pigment Reacted with3-Aminopropyl(3-oxobutaonoic)acid Functionalized Silica Nanoparticlesand In-Situ Crosslinked by Polyamide Resin

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of REFLEX® 100 SparkleViolet R-706E (available from Creation of Quality Value Company Ltd.)suspended in 900 mL of deionized water and 100 mL of3-aminopropyl(3-oxobutaonoic)acid functionalized silica nanoparticles asa colloidal dispersion at 2.5 wt % loading in DMF (available fromMillipore Sigma). The mixture was heated to 40° C. with vigorousstirring for 4 hours to facilitate the adsorption of the silicananoparticles onto the surface of the pigment. The suspension is cooledto room temperature and filtered to remove the water and DMF solvent.The functionalized pigment particles with free carboxylic acidfunctional groups are dried in a vacuum oven at 40° C. for 24 hours toproduce a functionalized pigment powder.

A clear viscous stock solution (1.5 molar) of thionyl chloride (5.46 mL,0.075 mol) and benzotriazole (8.93 g, 0.075 mol) in 50 mL of drymethylene chloride was prepared at room temperature with mixing. Aportion of this solution (1.25 mmol) is added slowly to convert thependent carboxylic acid functional groups on the surface of the micapigment to acid chloride to enable curing with the amino polyamide groupin the polyamide resin.

The dried mica pigment REFLEX® 100 Sparkle Violet R-706E functionalizedwith surface carboxylic acid (approximately 110 g) is suspended in 500mL of dry methylene chloride with constant agitation. To this mixture isadded 20 mL of the thionyl chloride-benzotriazole mixture slowly over 30minutes at room temperature. As the reaction proceeds benzotriazolehydrochloride salt starts to precipitate out of the solution indicatingthe conversion of the carboxylic acid is converted to the acid chloride.The reaction mixture is mixed for an additional 30 minutes and then themixture is filtered to remove the solvent and thoroughly washed withwater then dried in a vacuum oven for 24 hours.

Subsequently, 50 g of polyamide resin such as nylon 6,6 is melt mixedwith 10 g of the above acid chloride surface functionalized mica pigmentReflex® 100 Sparkle Violet R-706E melt mixed in the Haake mixer at 150°C. to 200° C. for 20 to 30 minutes to facilitate the crosslinkingreaction of the acid chloride with the amino group of the polyamideresin. The resulting pigment-pendent polyamide resin concentrate isdischarged from the Haake mixer, cooled and grounded into a fine powderfor subsequent incorporation into pigmented polyamide micron particles.

Using 30 g of REFLEX® 100 Sparkle Violet R-706E pigment-pendentcrosslinked polyamide resin onto the pigment surface and 570 g of nylon6,6 is melt mixed with 2000 g of polydimethylsiloxane (PDMS) of 20,000specific viscosity by hot melt emulsification in a 25 mm twin-screwextruder (Werner & Pfleiderer ZSK-25). The polymer pellets are added tothe extruder first, brought to the temperature of 230° C. and rpm of1100, and then preheated carrier fluid having AEROSIL® R812S silicananoparticles (1.1 wt % relative to PP-polyamide) dispersed therein isadded to the molten polymer in the extruder

Then the mixture is discharged into a container and allowed to cool toroom temperature over several hours. The resultant mixture is thenfiltered through a 90 mm WHATMAN® #1 paper filter (available fromSigmaAldrich) to separate the PP-polyamides particles from the carrierfluid. The particles are washed three times with 2000 mL of ethylacetate. The particles are then allowed to dry overnight in vacuum ovenat ambient temperature. Optionally, the dried particles can be screenedthrough a 150-μm sieve. The PP-polyamide particles are thencharacterized for size with a Malvern MASTERSIZER™ 3000 and morphologywith SEM micrographs. The D50 (μm) is predicted to be around 55 μm witha span of about 1.30.

Prophetic Example 8: REFLEX® Glitter Blue R-781E Pigment Reacted with3-Aminopropyl(3-oxobutaonoic)acid Functionalized Silica Nanoparticlesand In-Situ Crosslinked by Polyamide Resin

Into a 2 liter glass reactor equipped with an overhead mechanicalstirrer and a heating mantle is added 100 g of REFLEX® Glitter Bluepigment, product code R-781E (available from Creation of Quality ValueCompany Ltd.) suspended in 900 mL of deionized water and 100 mL of3-aminopropyl(3-oxobutaonoic)acid functionalized silica nanoparticles asa colloidal dispersion at 2.5 wt % loading in DMF (available fromMillipore Sigma). The mixture was heated to 40° C. with vigorousstirring for 4 hours to facilitate the adsorption of the silicananoparticles onto the surface of the pigment. The suspension is cooledto room temperature and filtered to remove the water and DMF solvent.The functionalized pigment particles with free carboxylic acidfunctional groups are dried in a vacuum oven at 40° C. for 24 hours toproduce a functionalized pigment powder.

A clear viscous stock solution (1.5 molar) of thionyl chloride (5.46 mL,0.075 mol) and benzotriazole (8.93 g, 0.075 mol) in 50 mL of drymethylene chloride was prepared at room temperature with mixing. Aportion of this solution (1.25 mmol) is added slowly to convert thependent carboxylic acid functional groups on the surface of the micapigment to acid chloride to enable curing with the amino polyamide groupin the polyamide resin.

The dried mica pigment REFLEX® Glitter Blue functionalized with surfacecarboxylic acid (approximately 110 g) is suspended in 500 mL of drymethylene chloride with constant agitation. To this mixture is added 20mL of the thionyl chloride-benzotriazole mixture slowly over 30 minutesat room temperature. As the reaction proceeds benzotriazolehydrochloride salt starts to precipitate out of the solution indicatingthe conversion of the carboxylic acid is converted to the acid chloride.The reaction mixture is mixed for an additional 30 minutes and then themixture is filtered to remove the solvent and thoroughly washed withwater then dried in a vacuum oven for 24 hours.

Subsequently, 50 g of polyamide resin such as nylon 6,6 is melt mixedwith 10 g of the above acid chloride surface functionalized mica pigmentReflex® Glitter Blue melt mixed in the Haake mixer at 150° C. to 200° C.for 20 to 30 minutes to facilitate the crosslinking reaction of the acidchloride with the amino group of the polyamide resin. The resultingpigment-pendent polyamide resin concentrate is discharged from the Haakemixer, cooled and grounded into a fine powder for subsequentincorporation into pigmented polyamide micron particles.

Using 1.5 g of Reflex® Glitter Blue pigment-pendent crosslinkedpolyamide resin onto the pigment surface and 28.5 g of Nylon 6,6 is meltmixed with 150 g of polydimethylsiloxane (PDMS) of 60,000 specificviscosity containing AEROSIL® R812S silica nanoparticles (0.75 wt %relative to PP-polyamide) dispersed therein by hot melt emulsificationin a Haake mixer fitted with a 300 ml mixing vessel. The mixer is heatedto 230° C. and mixed at 200 rpm for 20 minutes.

Then, the mixture is discharged from the Haake onto a cold surface toprovide rapid quench cooling. The resultant mixture is then filteredthrough a 90 mm WHATMAN® #1 paper filter (available from SigmaAldrich)to separate the PP-polyamides particles from the carrier fluid. Theparticles are washed three times with 1000 mL of ethyl acetate. Theparticles are then allowed to air dry overnight in an aluminum pan in afume hood. Optionally, the dried particles can be screened through a150-μm sieve. The PP-polyamide particles are then characterized for sizewith a Malvern MASTERSIZER™ 3000 and morphology with SEM micrographs.The D50 (μm) is predicted to be around 75 μm with a span of about 0.85.

Prophetic Example 9: General Epoxide and Polyamide Reaction Conditions

The epoxide group on the metallic pigment reactions with the polyamidemay be performed under an atmosphere (nitrogen or argon) at temperaturesof about 70° C. to about 200° C. (or about 70° C. to about 150° C.,about 125° C. to about 200° C.) in the presence of an organic solventsuch as tetrahydrofuan, dimethylformamide, toluene, and the like, andany combination thereof. The mixture is then stirred for about 24 hoursat an elevated temperature. After cooling the mixture to roomtemperature, the grafted polymer is filtered and washed to removeorganic impurities and unreacted starting reagents.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Theparticular examples and configurations disclosed above are illustrativeonly, as the present invention may be modified and practiced indifferent but equivalent manners apparent to those skilled in the arthaving the benefit of the teachings herein. Furthermore, no limitationsare intended to the details of construction or design herein shown,other than as described in the claims below. It is therefore evidentthat the particular illustrative examples disclosed above may bealtered, combined, or modified and all such variations are consideredwithin the scope and spirit of the present invention. The inventionillustratively disclosed herein suitably may be practiced in the absenceof any element that is not specifically disclosed herein and/or anyoptional element disclosed herein. While compositions and methods aredescribed in terms of “comprising,” “containing,” or “including” variouscomponents or steps, the compositions and methods can also “consistessentially of” or “consist of” the various components and steps. Allnumbers and ranges disclosed above may vary by some amount. Whenever anumerical range with a lower limit and an upper limit is disclosed, anynumber and any included range falling within the range is specificallydisclosed. In particular, every range of values (of the form, “fromabout a to about b,” or, equivalently, “from approximately a to b,” or,equivalently, “from approximately a-b”) disclosed herein is to beunderstood to set forth every number and range encompassed within thebroader range of values. Also, the terms in the claims have their plain,ordinary meaning unless otherwise explicitly and clearly defined by thepatentee. Moreover, the indefinite articles “a” or “an,” as used in theclaims, are defined herein to mean one or more than one of the elementthat it introduces.

The invention claimed is:
 1. A method comprising: functionalizing metaloxide particles that are bound to a pigment particle with a silicaparticle having a carboxylic acid surface treatment to produce a surfacetreated pigment having a pendent carboxylic acid; converting the pendentcarboxylic acid to a pendent acid chloride; and reacting the pendentacid chloride with a polyamide to yield a pigment-pendent polyamide(PP-polyamide).
 2. The method of claim 1, wherein the metal oxideparticles comprise one or more selected from the group consisting of:titanium dioxide, a titanium suboxide, a titanium oxynitride, Al₂O₃,Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO, zirconium oxide, and an irontitanium oxide.
 3. The method of claim 1, wherein the pigment particlecomprises one or more selected from the group consisting of: syntheticmica, natural mica, talc, sericite, kaolin, glass, SiO₂ flakes, Al₂O₃flakes, glass flakes, acicular pigments, CaSO₄, iron oxides, chromiumoxides, carbon black, metal effect pigments, optically variablepigments, liquid crystal polymer pigments, and holographic pigments. 4.The method of claim 1, wherein the silica particle having the carboxylicacid surface treatment comprises one or more selected from the groupconsisting of: 3-aminopropyl-(3-oxobutanoic) acid functionalized silica,3-propylsulphonic acid-functionalized silica gel, propylcarboxylic acidfunctionalized silica, triaminetetraacetic acid-functionalized silicagel, propionyl chloride-functionalized silica gel, 3-carboxypropylfunctionalized silica gel, aminomethylphosphonic acid(AMPA)-functionalized silica gel, and1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid(DOTA)-functionalized silica gel.
 5. The method of claim 1, wherein thepolyamide is selected from the group consisting of: polycaproamide,poly(hexamethylene succinamide), polyhexamethylene adipamide,polypentamethylene adipamide, polyhexamethylene sebacamide,polyundecaamide, polydodecaamide, polyhexamethylene terephthalamide,nylon 10,10, nylon 10,12, nylon 10,14, nylon 10,18, nylon 6,18, nylon6,12, nylon 6,14, nylon 12,12, a semi-aromatic polyamide, an aromaticpolyamide, any copolymer thereof, and any combination thereof.
 6. Themethod of claim 1, wherein the reacting of the pendent acid chloridewith the polyamide comprises melt mixing the pigment particle having afunctionality with the pendent acid chloride with the polyamide for 15minutes to about 1 hour at about 125° C. to about 250° C.
 7. The methodof claim 1, wherein a weight ratio of the pigment to the polyamide isabout 1:10 to about 1:1000.
 8. A composition comprising: a polyamidehaving a pigment pendent from a backbone of the polyamide, wherein thepigment comprises metal oxide particles on the surface of a pigmentparticle.
 9. The composition of claim 8, wherein the polyamide isselected from the group consisting of: polycaproamide,poly(hexamethylene succinamide), polyhexamethylene adipamide,polypentamethylene adipamide, polyhexamethylene sebacamide,polyundecaamide, polydodecaamide, polyhexamethylene terephthalamide,nylon 10,10, nylon 10,12, nylon 10,14, nylon 10,18, nylon 6,18, nylon6,12, nylon 6,14, nylon 12,12, a semi-aromatic polyamide, an aromaticpolyamide, any copolymer thereof, and any combination thereof.
 10. Thecomposition of claim 8, wherein a weight ratio of the pigment to thepolyamide is about 1:10 to about 1:1000.
 11. The composition of claim 8,wherein the pigment particle comprises one or more selected from thegroup consisting of: synthetic mica, natural mica, talc, sericite,kaolin, glass, SiO₂ flakes, Al₂O₃ flakes, glass flakes, acicularpigments, CaSO₄, iron oxides, chromium oxides, carbon black, metaleffect pigments, optically variable pigments, liquid crystal polymerpigments, and holographic pigments.
 12. An article comprising: thecomposition of claim
 8. 13. The composition of claim 8, wherein themetal oxide particles comprise one or more selected from the groupconsisting of: titanium dioxide, a titanium suboxide, a titaniumoxynitride, Al₂O₃, Fe₂O₃, Fe₃O₄, SnO₂, ZnO, CuO, NiO, zirconium oxide,and an iron titanium oxide.